Asymmetric ANSA-metallocene catalyst compounds for producing polyolefins having a broad molecular weight distribution

ABSTRACT

The present disclosure relates to asymmetric ansa-metallocene catalyst compounds that include at least one indenyl ligand substituted at the 3-position with a C3-C40 α-branched alkyl, such as 1-methylethyl, 1-methylpropyl, 1-methylbutyl, 1-ethylbutyl, 1,3-dimethylbutyl, 1-methyl-1-ethylbutyl, 1,1-diethylbutyl, 1-propylpentyl, and the like. Catalyst systems prepared with the catalyst compounds, polymerization methods using such catalyst systems, and polyolefins made using the polymerization methods are also described.

PRIORITY CLAIM

This application claims priority to and the benefit of U.S. Ser. No. 62/592,217, filed Nov. 29, 2017 and is incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

The present disclosure relates to ansa-metallocene catalyst compounds, to catalyst systems comprising such compounds, and to uses thereof.

BACKGROUND OF THE INVENTION

Polyolefins are widely used commercially because of their robust physical properties. For example, various types of polyethylenes, including high density, low density, and linear low density polyethylenes, are some of the most commercially useful. Polyolefins are typically prepared with a catalyst that polymerizes olefin monomers.

Catalysts for olefin polymerization typically have transition metals. For example, some catalysts are ansa-metallocenes, i.e., “bridged” metallocenes, which can be activated by alumoxane or an activator containing a non-coordinating anion. Using these catalysts and catalyst systems, polymerization conditions can be adjusted to provide polyolefins having desired properties. There is interest in finding new metallocene catalysts and catalyst systems that provide polymers having specific properties, including high molecular weights, increased conversion or comonomer incorporation, good processability, and uniform comonomer distribution. In particular, there is a need for catalyst systems capable of producing polyolefins, including linear low density polyethylene, having a broad and/or bimodal molecular weight distribution and an improved balance of processability and toughness.

Some metallocene catalyst systems, sometimes referred to as “dual” catalyst systems, utilize a combination of two different metallocene catalyst compounds to produce polyethylene having a broad and/or bimodal molecular weight distribution. For example, U.S. Pat. Nos. 8,865,846 and 9,273,159 describe dual catalyst systems for producing broad molecular weight distribution polymers. The polymerization processes disclosed therein are said to be for the production of olefin polymers and the disclosed processes can use a dual catalyst system containing a zirconium or hafnium-based metallocene compound and a titanium-based half-metallocene compound containing an indenyl group.

It may be desirable, however, to produce polyolefins, including linear low density polyethylene having a broad and/or bimodal molecular weight distribution, with a catalyst system that utilizes a single catalyst compound, i.e., a catalyst compound corresponding to a single structural formula (although such a catalyst compound may comprise and be used as a mixture of isomers, e.g., stereoisomers). For example, U.S. Pat. Nos. 6,136,936 and 6,664,351 disclose ethylene copolymers with a wide molecular weight distribution and a process and catalyst system for preparing them. Linear low density polyethylene copolymers having a uniform distribution of comonomer units along the polymer chain and a broad molecular weight distribution are said to be achievable by carrying out the polymerization reaction in the presence of a catalyst consisting of a mixture of the racemic and meso isomers of a stereorigid metallocene compound. Examples utilizing mixtures of rac/meso-ethylene-bis(4,7-dimethyl-1-indenyl)zirconium dichloride are shown to produce ethylene/1-olefin copolymers having densities from 0.9062 to 0.9276 g/ml and Mw/Mn values from 3.7 to 8.1. Comparative examples utilizing rac-ethylene-bis(4,7-dimethyl-1-indenyl)zirconium dichloride were shown to produce copolymers having densities of 0.9055 and 0.9112 g/ml and Mw/Mn values of 2.3 and 2.9.

U.S. Pat. Nos. 5,914,289 and 6,225,428 disclose the production of high density polyethylene homopolymers or copolymers having a broad and monomodal molecular weight distribution. The disclosed polymerization process is said to be conducted in the presence of supported metallocene-alumoxane catalysts wherein the metallocene consists of a particular bridged meso or racemic stereoisomer, preferably the racemic stereoisomers. The metallocenes used are said to comprise at least a hydrogenated indenyl or fluorenyl that it is isolated on its support under the form of all its conformers. Examples utilizing ethylenebis(4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride or ethylenebis(indenyl) zirconium dichloride are shown to produce polymers having molecular weight distribution values of 7.4 and 6.3.

US 2006/0142147 discloses a series of bridged indenyl metallocenes substituted at the 3 position, a catalyst system containing the bridged indenyl metallocenes, and a polymerization process using such catalyst system. Polyethylene copolymers made with the catalysts are said to have narrow to broad bimodal molecular weight distributions depending on proper selection of the indenyl substituent, the number of substituents, and the type of stereoisomeric form used: pure (racemic or meso) or mixtures thereof. Examples utilizing the catalysts are shown to produce copolymers having Mw/Mn values of from 1.87 to 21.7.

Controlling the type and location of substitution on ansa-metallocene compounds so as to potentially control the properties of the polyolefins prepared with the metallocene is of interest. Synthetic routes to substituted metallocene catalysts are known. For example, Balboni, et al., in Macromolecular Chemistry and Physics, 2001, 202, pp. 2010-2028, disclose synthetic routes to C₂-symmetric ansa-zirconocene catalysts having 3-isopropyl substituents on the indenyl rings. In WO 2017/010648 metallocene catalyst compounds based on substituted bis(indenyl) zirconium chloride compounds having branched and/or unbranched alkyl groups at various positions on the indenyl rings are disclosed (see, e.g., formula 33 of claim 14 on page 51).

Additional references of interest include: CN 103641862A; EP 0849273; EP 2003166; U.S. Pat. Nos. 5,447,895; 6,569,965; 6,573,350; 7,026,494; 7,297,653; 7,799,879; 8,288,487; 8,324,126; 8,404,880; 8,598,061; 8,609,793; 8,637,616; 8,975,209; 9,040,642; 9,040,643; 9,102,821; 9,340,630; US 2012/0088890; US 2014/0057777; US 2014/0107301; WO 2013/151863; WO 2016/094843; WO 2016/171807; WO 2016/171809; WO 2016/172099; WO 2016/195424; WO 2016/196331; Araneda, et al., Inorganica Chimica Acta, 434, 2005, pp. 121-126; Perez-Camacho, et al., Journal of Organometallic Chemistry, 1999, Vol. 585, pp. 18-25; and Ryabov, et al., Organometallics, 2009, Vol. 28, pp. 3614-3617.

This invention also relates to commonly owned applications U.S. Ser. No. 62/446,007 filed on Jan. 13, 2017, and 62/404,506 filed Oct. 5, 2016, and U.S. Ser. No. 62/592,228 filed on Nov. 29, 2017.

There is still a need for new catalyst systems that utilize a single catalyst compound and produce polyolefins having a broad and/or bimodal molecular weight distribution (MWD). Such catalyst compounds and catalyst systems utilizing them, and processes for the polymerization of olefins using such compounds and systems, are disclosed herein.

SUMMARY OF THE INVENTION

The present disclosure relates to asymmetric ansa-metallocene catalyst compounds represented by Formula (I):

where M is a group 4 metal, R³ is a C₃-C₄₀ branched alkyl, wherein the branched alkyl group is branched at the α-position, R^(3′) is hydrogen, methyl, ethyl, or a group containing three or more carbon atoms having the formula —CH₂R′, where R′ is an alkyl, aryl, or silyl group; each of R², R⁴, R⁵, R⁶, R⁷, R^(2′), R^(4′), R^(5′), R^(6′), and R^(7′) is independently hydrogen or a C₁-C₄₀ substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, alkoxyl, halogen, or siloxyl, and one or more of R⁴ and R⁵, R⁵ and R⁶, R⁶ and R⁷, R^(4′) and R^(5′), R^(5′) and R^(6′), and R^(6′) and R^(7′) are joined to form a completely saturated, partially saturated, or aromatic ring, T is a bridging group, and each X is independently a halide or C₁-C₅₀ substituted or unsubstituted hydrocarbyl, hydride, amide, alkoxide, sulfide, phosphide, halide, or a combination thereof, or two of X are joined together to form a metallocycle ring, or two of X are joined to form a chelating ligand, a diene ligand, or an alkylidene.

In yet another aspect, embodiments of the present disclosure provide a catalyst system comprising an activator and a catalyst compound of the present disclosure.

In still another aspect, embodiments of the present disclosure provide a polymerization process comprising a) contacting one or more olefin monomers with a catalyst system comprising: i) an activator and ii) a catalyst compound of the present disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plot of polydispersity index versus 1-hexene incorporation for polyethylenes prepared with the catalyst systems of Examples 1 and 2 and comparative Examples 3-6.

FIG. 2 is a plot of 1-hexene feed versus 1-hexene incorporation for polyethylenes prepared with the catalyst systems of Examples 1 and 2 and comparative Example 3.

FIG. 3 is a plot of polydispersity index versus 1-hexene feed for polyethylenes prepared with the catalyst systems of Examples 1 and 7 and comparative Example 8.

FIG. 4 is a plot of weight average molecular weight (Mw) versus 1-hexene feed for polyethylenes prepared with the catalyst systems of Examples 1 and 7.

FIG. 5 is a plot of weight average molecular weight (Mw) versus 1-hexene feed for polyethylenes prepared with the catalyst systems of Examples 9, 10, and 11 and comparative Example 8.

FIG. 6 is a plot of weight average molecular weight (Mw) versus 1-hexene feed for polyethylenes prepared with the catalyst systems of Examples 9, 10, and 11.

FIG. 7A is a graph showing GPC-4D data for the polyethylene prepared according to Example 15.

FIG. 7B is a graph showing GPC-4D data for the polyethylene prepared according to Example 16.

FIG. 7C is a graph showing GPC-4D data for the polyethylene prepared according to Example 17.

FIG. 7D is a graph showing GPC-4D data for the polyethylene prepared according to Example 18.

FIG. 8A is a contour plot of CFC data for the polyethylene prepared according to Example 15.

FIG. 8B is a 3D plot of CFC data for the polyethylene prepared according to Example 15.

FIG. 9A is a contour plot of CFC data for the polyethylene prepared according to Example 19.

FIG. 9B is a 3D plot of CFC data for the polyethylene prepared according to Example 19.

FIG. 10A is a contour plot of CFC data for the polyethylene prepared according to Example 18.

FIG. 10B is a 3D plot of CFC data for the polyethylene prepared according to Example 18.

FIG. 11A is a contour plot of CFC data for the polyethylene prepared according to Example 36.

FIG. 11B is a 3D plot of CFC data for the polyethylene prepared according to Example 36.

FIG. 12A is a contour plot of CFC data for the polyethylene prepared according to Example 38.

FIG. 12B is a 3D plot of CFC data for the polyethylene prepared according to Example 38.

FIG. 13 is a graph showing second melt DSC of polyethylene prepared according to Example 18.

FIG. 14A is a graph showing Extensional rheology recorded at 130° C. for the polyethylene prepared according to Example 18.

FIG. 14B is a graph showing Extensional rheology recorded at 150° C. for the polyethylene prepared according to Example 18.

DEFINITIONS AND CONVENTIONS

For the purposes of this disclosure and the claims herein, the definitions and conventions below shall apply.

The numbering scheme for the Periodic Table Groups is used as described in CHEMICAL AND ENGINEERING NEWS, 63(5), pg. 27 (1985). Therefore, a “group 4 metal” is an element from group 4 of the Periodic Table, e.g., Ti, Zr, and Hf.

“Catalyst activity” is a measure of how many grams of polymer (P) are produced using a polymerization catalyst comprising W g of catalyst (cat), over a period of time of T hours; and may be expressed by the following formula: P/(T×W) and expressed in units of gP·gcat⁻¹hr⁻¹.

An “olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of this specification and the claims appended thereto, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an “ethylene” content of 35 weight % to 55 weight % (i.e., 35 weight % to 55 weight %), it is understood that the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 weight % to 55 weight %, based upon the weight of the copolymer.

A “polymer” has two or more of the same or different mer units. A “homopolymer” is a polymer having mer units that are the same. A “copolymer” is a polymer having two or more mer units that are different from each other.

As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, and Mz is z average molecular weight, wt % is weight percent, and mol % is mole percent. Molecular weight distribution (MWD), also referred to as polydispersity or polydispersity index (PDI), is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weight units (e.g., Mw, Mn, Mz) are g/mol.

The following abbreviations may be used herein: Me is methyl, Et is ethyl, Pr is propyl, nPr is n-propyl, iPr is isopropyl, Bu is butyl, nBu is normal butyl, iBu is isobutyl, sBu is sec-butyl, tBu is tert-butyl, Oct is octyl, Ph is phenyl, Bn is benzyl, MAO is methylalumoxane.

In chemical or structural formulas, when an “R” group, such as R^(x), R^(y), R^(z), R^(a), R⁴, R⁴ or the like is said to be “hydrogen,” it will be understood as a reference to the —H group rather than elemental hydrogen (H₂).

A “catalyst system” is a combination of at least one catalyst compound, at least one activator, an optional co-activator, and an optional support material. When catalyst systems are described as comprising neutral stable forms of the components, it will be understood that the ionic form of the component is the form that reacts with the monomers to produce polymers.

An “anionic ligand” is a negatively charged ligand that donates one or more pairs of electrons to a metal ion. A “neutral donor ligand” is a neutrally charged ligand which donates one or more pairs of electrons to a metal ion.

Except with respect to the term “substituted hydrocarbyl,” the term “substituted” means that at least one hydrogen atom has been replaced with at least one non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom containing group, such as halogen (such as Br, Cl, F or I) or at least one functional group such as —NR*₂, —OR*, —SeR*, —TeR*, —PR*₂, —AsR*₂, —SbR*₂, —SR*, —BR*₂, —SiR*₃, —GeR*₃, —SnR*₃, —PbR*₃, and the like, where each R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted completely saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure, or where at least one heteroatom has been inserted within a hydrocarbyl ring. As examples, methyl cyclopentadiene (Cp) is a Cp group substituted with a methyl group, and ethyl alcohol is an ethyl group substituted with an —OH group.

The terms “group,” “radical,” and “substituent” may be used interchangeably.

The term “hydrocarbyl” is defined to be a C₁-C₁₀₀ radical that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic. Examples of such radicals include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like. Substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom of the hydrocarbyl radical has been substituted with at least one non-hydrogen group, such as another hydrocarbyl group (e.g., phenyl), which may impart a branch to the hydrocarbyl group, or substituted with a heteroatom or heteroatom-containing group, such as halogen (e.g., Br, Cl, F or I), or at least one functional group such as —NR*₂, —OR*, —SeR*, —TeR*, —PR*₂, —AsR*₂, —SbR*₂, —SR*, —BR*₂, —SiR*₃, —GeR*₃, —SnR*₃, —PbR*₃, and the like, or where at least one heteroatom has been inserted within a hydrocarbyl ring.

The term “single catalyst compound” refers to a catalyst compound corresponding to a single structural formula, although such a catalyst compound may comprise and be used as a mixture of isomers, e.g., stereoisomers.

A catalyst system that utilizes a single catalyst compound means a catalyst system that is prepared using only a single catalyst compound in the preparation of the catalyst system. Thus, such a catalyst system is distinguished from, for example, “dual” catalyst systems, which are prepared using two catalyst compounds having different structural formulas, i.e., the connectivity between the atoms, the number of atoms, and/or the type of atoms in the two catalyst compounds is different. Thus, one catalyst compound is considered different from another if it differs by at least one atom, either by number, type, or connection. For example “bisindenyl zirconium dichloride” is different from (indenyl)(2-methylindenyl) zirconium dichloride” which is different from “(indenyl)(2-methylindenyl) hafnium dichloride.” Catalyst compounds that differ only in that they are stereoisomers of each other are not considered to be different catalyst compounds. For example, rac-dimethylsilylbis(2-methyl 4-phenyl)hafnium dimethyl and meso-dimethylsilylbis(2-methyl 4-phenyl)hafnium dimethyl are considered to be not different.

The terms “cocatalyst” and “activator” are used herein interchangeably and are defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral catalyst compound to a catalytically active catalyst compound cation.

Noncoordinating anion (NCA) means an anion either that does not coordinate to the catalyst metal cation or that does coordinate to the metal cation, but only weakly. The term NCA is also defined to include multicomponent NCA-containing activators, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, that contain an acidic cationic group and the non-coordinating anion. The term NCA is also defined to include neutral Lewis acids, such as tris(pentafluorophenyl)boron, that can react with a catalyst to form an activated species by abstraction of an anionic group. An NCA coordinates weakly enough that a neutral Lewis base, such as an olefinically or acetylenically unsaturated monomer can displace it from the catalyst center. Any metal or metalloid that can form a compatible, weakly coordinating complex may be used or contained in the noncoordinating anion. Suitable metals include, but are not limited to, aluminum, gold, and platinum. Suitable metalloids include, but are not limited to, boron, aluminum, phosphorus, and silicon. The term non-coordinating anion activator includes neutral activators, ionic activators, and Lewis acid activators. The terms “non-coordinating anion activator” and “ionizing activator” are used interchangeably herein.

The terms “process” and “method” are used interchangeably.

Additional definitions and conventions may be set forth below in other portions of the present disclosure.

DETAILED DESCRIPTION

This disclosure relates to asymmetric ansa-metallocene catalyst compounds represented by Formula (I) and to catalyst systems and polymerization methods utilizing such asymmetric ansa-metallocene catalyst compounds:

In Formula (I), M is a group 4 metal, preferably titanium (Ti), zirconium (Zr), or hafnium (Hf), R³ is a C₃-C₄₀ branched alkyl group, wherein the branched alkyl group is branched at the α-position, R^(3′) is hydrogen, methyl, ethyl, or a group containing three or more carbon atoms having the formula —CH₂R′, where R′ is an alkyl, aryl, or silyl group, each of R², R⁴, R⁵, R⁶, R⁷, R^(2′), R^(4′), R^(5′), R^(6′), and R^(7′) is independently hydrogen or a C₁-C₄₀ substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, alkoxyl, halogen, or siloxyl, or one or more of R⁴ and R⁵, R⁵ and R⁶, R⁶ and R⁷, R^(4′) and R^(5′), R^(5′) and R^(6′), and R^(6′) and R^(7′) are joined to form a completely saturated, partially saturated, or aromatic ring, T represents the formula R⁸ ₂J or (R⁸)J₂, where J is C, Si, or Ge, and each R⁸ is independently hydrogen, halogen, a C₁ to C₄₀ hydrocarbyl or a C₁ to C₄₀ substituted hydrocarbyl group, and two R⁸ can form a cyclic structure including completely saturated, partially saturated, aromatic, or fused ring systems, and each X is independently a halide or C₁-C₅₀ substituted or unsubstituted hydrocarbyl, hydride, amide, alkoxide, sulfide, phosphide, halide, or a combination thereof, or two of X are joined together to form a metallocycle ring, or two of X are joined to form a chelating ligand, a diene ligand, or an alkylidene. Suitable examples of C₃-C₄₀ alkyls branched at the α-position include 1-methylethyl, 1-methylpropyl, 1-methylbutyl, 1-ethylbutyl, 1,3-dimethylbutyl, 1-methyl-1-ethylbutyl, 1,1-diethylbutyl, 1-propylpentyl, 1-phenylethyl, i-propyl, 2-butyl, sec-pentyl, sec-hexyl, and the like.

In one embodiment, R³ is a C₃-C₄₀ branched alkyl represented by Formula (II):

where each R^(z) and R^(x) is, independently, a C₁ to C₂₀ alkyl group and R^(y) is hydrogen or a C₁ to C₄ alkyl group. Examples of suitable C₁ to C₂₀ alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and isomers thereof. Examples of suitable C₁ to C₄ groups include methyl, ethyl, propyl, and butyl, and isomers thereof. The C₁ to C₄ alkyl group in Formula (II) is preferably a C₁ to C₂ alkyl group. In a preferred embodiment, R^(y) in Formula (II) above is hydrogen, such that R³ is represented by Formula (III) where R^(z) and R^(x) are as defined above for Formula (II):

In another embodiment, each R^(x), R^(y), and R^(z) is different from any other R^(x), R^(y), and R^(z) such that the catalyst compound has a chiral center on the α-carbon of R³. In a preferred embodiment, R³ is represented by Formula (III), R^(z) is n-propyl, R^(x) is methyl, and R^(3′) is hydrogen, methyl, ethyl, or a group containing three or more carbon atoms having the formula —CH₂R′, where R′ is an alkyl, aryl, or silyl group. In another preferred embodiment, R^(z) is n-propyl, R^(x) is methyl, and R^(3′) is methyl. In a further embodiment, the catalyst compound is as described in any of the foregoing embodiments and each of R², R⁴, R⁵, R⁶, R⁷, R^(2′), R^(4′), R^(5′), R^(6′), and R^(7′) is hydrogen.

In still another embodiment, one or more of adjacent groups R⁴ and R⁵, R⁵ and R⁶, R⁶ and R⁷, R^(4′) and R^(5′), R^(5′) and R^(6′), and R^(6′) and R^(7′) may be joined to form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated, or completely saturated. In a particularly preferred embodiment, R⁵ and R⁶ are joined to form a partially saturated 5-membered ring, such that a 3-substituted 1,5,6,7-tetrahydro-s-indacenyl group is formed. In a preferred embodiment, the 1,5,6,7-tetrahydro-s-indacenyl group is substituted at the 3-position with a 2-pentyl group.

In yet other embodiments, “J” in the catalyst compound of any of the foregoing embodiments is Si and R⁸ is a C₁ to C₄₀ hydrocarbyl or a C₁ to C₄₀ substituted hydrocarbyl group. In such embodiments each R⁸ is preferably a methyl group.

In yet other embodiments, “M” in any of the catalyst compounds of the foregoing embodiments is Ti, Zr, or Hf, preferably Zr.

In yet other embodiments, each “X” in any of the catalyst compounds of the foregoing embodiments is a halide, preferably chloride.

In any embodiment of the invention, T is a bridging group containing at least one Group 13, 14, 15, or 16 element, in particular boron or a Group 14, 15, or 16 element. Examples of suitable bridging groups include P(═S)R*, P(═Se)R*, P(═O)R*, R*₂C, R*₂Si, R*₂Ge, R*₂CCR*₂, R*₂CCR*₂CR*₂, R*₂CCR*₂CR*₂CR*₂, R*C═CR*, R*C═CR*CR*₂, R*₂CCR*═CR*CR*₂, R*C═CR*CR*═CR*, R*C═CR*CR*₂CR*₂, R*₂CSiR*₂, R*₂SiSiR*₂, R*₂SiOSiR*₂, R*₂CSiR*₂CR*₂, R*₂SiCR*₂SiR*₂, R*C═CR*SiR*₂, R*₂CGeR*₂, R*₂GeGeR*₂, R*₂CGeR*₂CR*₂, R*₂GeCR*₂GeR*₂, R*₂SiGeR*₂, R*C═CR*GeR*₂, R*B, R*₂C—BR*, R*₂C—BR*—CR*₂, R*₂C—O—CR*₂, R*₂CR*₂C—O—CR*₂CR*₂, R*₂C—O—CR*₂CR*₂, R*₂C—O—CR*═CR*, R*₂C—S—CR*₂, R*₂CR*₂C—S—CR*₂CR*₂, R*₂C—S—CR*₂CR*₂, R*₂C—S—CR*═CR*, R*₂C—Se—CR*₂, R*₂CR*₂C—Se—CR*₂CR*₂, R*₂C—Se—CR*₂CR*₂, R*₂C—Se—CR*═CR*, R*₂C—N═CR*, R*₂C—NR*—CR*₂, R*₂C—NR*—CR*₂CR*₂, R*₂C—NR*—CR*═CR*, R*₂CR*₂C—NR*—CR*₂CR*₂, R*₂C—P═CR*, R*₂C—PR*—CR*₂, O, S, Se, Te, NR*, PR*, AsR*, SbR*, O—O, S—S, R*N—NR*, R*P—PR*, O—S, O—NR*, O—PR*, S—NR*, S—PR*, and R*N—PR* where R* is hydrogen or a C₁-C₂₀ containing hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl substituent and optionally two or more adjacent R* may join to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent. Preferred examples for the bridging group T include CH₂, CH₂CH₂, SiMe₂, SiPh₂, SiMePh, Si(CH₂)₃, Si(CH₂)₄, O, S, NPh, PPh, NMe, PMe, NEt, NPr, NBu, PEt, PPr, Me₂SiOSiMe₂, and PBu. In a preferred embodiment of the invention in any embodiment of any formula described herein, T is represented by the formula ER^(d) ₂ or (ER^(d) ₂)₂, where E is C, Si, or Ge, and each R^(d) is, independently, hydrogen, halogen, C₁ to C₂₀ hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or a C₁ to C₂₀ substituted hydrocarbyl, and two R^(d) can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system. Preferably, T is a bridging group comprising carbon or silica, such as dialkylsilyl, preferably T is selected from CH₂, CH₂CH₂, C(CH₃)₂, SiMe₂, Me₂Si—SiMe₂, cyclotrimethylenesilylene (Si(CH₂)₃), cyclopentamethylenesilylene (Si(CH₂)₅) and cyclotetramethylenesilylene (Si(CH₂)₄).

Preferably, T represents the formula R⁸ ₂J or (R⁸)J₂, where each J is independently selected from C, Si, or Ge, and each R⁸ is independently hydrogen, halogen, a C₁ to C₄₀ hydrocarbyl or a C₁ to C₄₀ substituted hydrocarbyl group, and two R⁸ can form a cyclic structure including completely saturated, partially saturated, aromatic, or fused ring systems.

In still other embodiments, the catalyst compound represented by Formula (I) corresponds to any one of the structures shown in Table 1:

TABLE 1 Catalyst Compound Structures 1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

46

47

48

49

50

Methods of Preparing the Catalyst Compounds

All air sensitive syntheses are carried out in nitrogen purged dry boxes. All solvents are available from commercial sources. Aluminum alkyls are available as hydrocarbon solutions from commercial sources. Methylalumoxane (“MAO”) is available from Albemarle as a 30 wt % solution in toluene. Generally, the catalyst compounds of this disclosure may be synthesized according to the schematic reaction procedure described in, for example, WO 2016196331 in paragraph [0080], where (i) is a deprotonation via a metal salt of alkyl anion (e.g., n-BuLi) to form an indenide; (ii) is reaction of indenide with an appropriate bridging precursor (e.g., Me₂SiCl₂); (iii) is reaction of the above product with AgOTf; (iv) is reaction of the above triflate compound with another equivalent of indenide; (v) is deprotonation via an alkyl anion (e.g., n-BuLi) to form a dianion; (vi) is reaction of the dianion with a metal halide (e.g., ZrCl₄).

Catalyst Systems

In one or more embodiments, the catalyst system of the present disclosure comprises an activator and any of the catalyst compounds described above. While the catalyst systems of the present disclosure may utilize any of the catalyst compounds described above in combination with each other or with one or more catalyst compounds not described above, in a preferred embodiment the catalyst systems utilize a single catalyst compound corresponding one of the catalyst compounds of the present disclosure. In yet other embodiments, the catalyst system is as described in any of the foregoing embodiments, wherein the catalyst system comprises a support material. In still other embodiments, the catalyst system is as described in any of the foregoing embodiments, wherein the support material is silica. In still further embodiments, the catalyst system is as described in any of the foregoing embodiments, wherein the activator comprises one or more of alumoxanes, aluminum alkyls, and ionizing activators.

In another embodiment, the present disclosure relates to a method for preparing a catalyst system comprising the step of contacting the catalyst compound of any of the embodiments described above with an activator, wherein said catalyst compound is a single catalyst compound and said single catalyst compound is the only catalyst compound contacted by an activator in said method. In yet another embodiment, the present disclosure relates to a method of polymerizing olefins comprising contacting at least one olefin with said catalyst system and obtaining a polyolefin. In still another embodiment, the present disclosure relates to a method of polymerizing olefins comprising contacting two or more different olefins with said catalyst system and obtaining a polyolefin. In a further embodiment, the present disclosure relates to a catalyst system comprising the catalyst compound of any of the embodiments described above, wherein said catalyst system consists of a single catalyst compound. In a still further embodiment, the present disclosure relates to a catalyst system comprising the catalyst compound of any of the embodiments described above, wherein said catalyst system consists essentially of a single catalyst compound.

Activators

After the catalyst compounds have been synthesized, catalyst systems may be formed by combining them with activators in any suitable manner, including by supporting them for use in slurry or gas phase polymerization. The catalyst systems may also be added to or generated in solution polymerization or bulk polymerization (in the monomer, i.e., no solvent). The catalyst system typically comprises a catalyst compound as described above and an activator such as alumoxane or a non-coordinating anion activator (NCA). Activation may be performed using alumoxane solution including methyl alumoxane, referred to as MAO, as well as modified MAO, referred to herein as MMAO, which contains some higher alkyl groups to improve the solubility. MAO can be purchased from Albemarle Corporation, Baton Rouge, La., typically in a 10 wt % solution in toluene. Another useful alumoxane is solid polymethylaluminoxane as described in U.S. Pat. Nos. 9,340,630; 8,404,880; and 8,975,209. The catalyst systems employed in the present disclosure can use an activator selected from alumoxanes, such as methyl alumoxane, modified methyl alumoxane, ethyl alumoxane, iso-butyl alumoxane, and the like. Alternatively, the catalyst systems can use activators that are aluminum alkyls or ionizing activators.

When an alumoxane or modified alumoxane is used, the catalyst compound-to-activator molar ratio is from about 1:3000 to about 10:1; such as about 1:2000 to about 10:1; such as about 1:1000 to about 10:1; such as about 1:500 to about 1:1; such as about 1:300 to about 1:1; such as about 1:200 to about 1:1; such as about 1:100 to about 1:1; such as about 1:50 to about 1:1; such as about 1:10 to about 1:1. When the activator is an alumoxane (modified or unmodified), some embodiments select the maximum amount of activator at a 5000-fold molar excess over the catalyst (per metal catalytic site). The minimum activator-to-catalyst ratio can be 1:1 molar ratio.

Activation may also be performed using non-coordinating anions, referred to as NCA's, of the type well known in the art. NCA may be added in the form of an ion pair using, for example, [DMAH]+[NCA]− in which the N,N-dimethylanilinium (DMAH) cation reacts with a basic leaving group on the transition metal complex to form a transition metal complex cation and [NCA]−. The cation in the precursor may, alternatively, be trityl. Alternatively, the transition metal complex may be reacted with a neutral NCA precursor, such as B(C₆F₅)₃, which abstracts an anionic group from the complex to form an activated species. Useful activators include N,N-dimethylanilinium tetrakis (pentafluorophenyl)borate (i.e., [PhNMe₂H]B(C₆F₅)₄) and N,N-dimethylanilinium tetrakis (heptafluoronaphthyl)borate, where Ph is phenyl, and Me is methyl.

In an embodiment of the present disclosure described herein, the non-coordinating anion activator is represented by the following formula (1): (Z)^(d+)(A^(d−))  (1) wherein Z is (L-H) or a reducible Lewis acid, L is a neutral Lewis base, H is hydrogen and (L-H)⁺ is a Bronsted acid; A^(d−) is a non-coordinating anion having the charge d−; and d is an integer from 1 to 3.

When Z is (L-H) such that the cation component is (L-H)^(d+), the cation component may include Bronsted acids such as protonated Lewis bases capable of protonating a moiety, such as an alkyl or aryl, from the catalyst precursor, resulting in a cationic transition metal species, or the activating cation (L-H)^(d+) is a Bronsted acid, capable of donating a proton to the catalyst precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof, or ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxoniums from ethers, such as dimethyl ether diethyl ether, tetrahydrofuran, and dioxane, sulfoniums from thioethers, such as diethyl thioethers and tetrahydrothiophene, and mixtures thereof.

When Z is a reducible Lewis acid, it may be represented by the formula: (Ar₃C+), where Ar is aryl or aryl substituted with a heteroatom, or a C₁ to C₄₀ hydrocarbyl, the reducible Lewis acid may be represented by the formula: (Ph₃C+), where Ph is phenyl or phenyl substituted with a heteroatom, and/or a C₁ to C₄₀ hydrocarbyl. In an embodiment, the reducible Lewis acid is triphenyl carbenium.

Embodiments of the anion component A^(d−) include those having the formula [M^(k)+Q^(n)]^(d−) wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6, or 3, 4, 5, or 6; n−k=d; M is an element selected from Group 13 of the Periodic Table of the Elements, or boron or aluminum, and Q is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl radicals, said Q having up to 20 carbon atoms with the proviso that in not more than one occurrence is Q a halide, and two Q groups may form a ring structure. Each Q may be a fluorinated hydrocarbyl radical having 1 to 20 carbon atoms, or each Q is a fluorinated aryl radical, or each Q is a pentafluoryl aryl radical. Examples of suitable Ad− components also include diboron compounds as disclosed in U.S. Pat. No. 5,447,895.

In an embodiment in any of the NCA's represented by Formula 1 described above, the anion component Ad− is represented by the formula [M*k*+Q*n*]d*- wherein k* is 1, 2, or 3; n* is 1, 2, 3, 4, 5, or 6 (or 1, 2, 3, or 4); n*−k*=d*; M* is boron; and Q* is independently selected from hydride, bridged or unbridged dialkylamido, halogen, alkoxide, aryloxide, hydrocarbyl radicals, said Q* having up to 20 carbon atoms with the proviso that in not more than 1 occurrence is Q* a halogen.

The present disclosure also relates to a method to polymerize olefins comprising contacting olefins (such as ethylene and 1-hexene) with a catalyst compound as described above and an NCA activator represented by the Formula (2): R_(n)M**(ArNHal)^(4-n)  (2) where R is a monoanionic ligand; M** is a Group 13 metal or metalloid; ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclic aromatic ring, or aromatic ring assembly in which two or more rings (or fused ring systems) are joined directly to one another or together; and n is 0, 1, 2, or 3. Typically the NCA comprising an anion of Formula 2 also comprises a suitable cation that is essentially non-interfering with the ionic catalyst complexes formed with the transition metal compounds, or the cation is Zd+ as described above.

In an embodiment in any of the NCA's comprising an anion represented by Formula 2 described above, R is selected from the group consisting of C₁ to C₃₀ hydrocarbyl radicals. In an embodiment, C₁ to C₃₀ hydrocarbyl radicals may be substituted with one or more C₁ to C₂₀ hydrocarbyl radicals, halide, hydrocarbyl substituted organometalloid, dialkylamido, alkoxy, aryloxy, alkysulfido, arylsulfido, alkylphosphido, arylphosphide, or other anionic substituent; fluoride; bulky alkoxides, where bulky means C₄ to C₂₀ hydrocarbyl radicals; —SRa, —NRa₂, and —PRa₂, where each Ra is independently a monovalent C₄ to C₂₀ hydrocarbyl radical comprising a molecular volume greater than or equal to the molecular volume of an isopropyl substitution or a C₄ to C₂₀ hydrocarbyl substituted organometalloid having a molecular volume greater than or equal to the molecular volume of an isopropyl substitution.

In an embodiment in any of the NCA's comprising an anion represented by Formula 2 described above, the NCA also comprises cation comprising a reducible Lewis acid represented by the formula: (Ar₃C+), where Ar is aryl or aryl substituted with a heteroatom, and/or a C₁ to C₄₀ hydrocarbyl, or the reducible Lewis acid represented by the formula: (Ph₃C+), where Ph is phenyl or phenyl substituted with one or more heteroatoms, and/or C₁ to C₄₀ hydrocarbyls.

In an embodiment in any of the NCA's comprising an anion represented by Formula 2 described above, the NCA may also comprise a cation represented by the formula, (L-H)^(d+), wherein L is an neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; and d is 1, 2, or 3, or (L-H)^(d+) is a Bronsted acid selected from ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof.

Further examples of useful activators include those disclosed in U.S. Pat. Nos. 7,297,653 and 7,799,879.

In an embodiment, an activator useful herein comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the Formula (3): (OX^(e+))_(d)(A^(d−))_(e)  (3) wherein OX^(e+) is a cationic oxidizing agent having a charge of e+; e is 1, 2 or 3; d is 1, 2 or 3; and A^(d−) is a non-coordinating anion having the charge of d− (as further described above). Examples of cationic oxidizing agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺². Suitable embodiments of Ad− include tetrakis(pentafluorophenyl)borate.

Activators useful in catalyst systems herein include: trimethylammonium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, trimethylammonium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, and the types disclosed in U.S. Pat. No. 7,297,653, which is fully incorporated by reference herein.

Suitable activators also include: N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, [Ph₃C⁺][B(C₆F₅)₄ ⁻], [Me₃NH⁺][B(C₆F₅)₄ ⁻]; 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium; and tetrakis(pentafluorophenyl)borate, 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

In at least one embodiment, the activator comprises a triaryl carbonium (such as triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

In at least one embodiment, two NCA activators may be used in the polymerization and the molar ratio of the first NCA activator to the second NCA activator can be any ratio. In at least one embodiment, the molar ratio of the first NCA activator to the second NCA activator is 0.01:1 to 10,000:1, or 0.1:1 to 1000:1, or 1:1 to 100:1.

In at least one embodiment, the NCA activator-to-catalyst ratio is a 1:1 molar ratio, or 0.1:1 to 100:1, or 0.5:1 to 200:1, or 1:1 to 500:1 or 1:1 to 1000:1. In at least one embodiment, the NCA activator-to-catalyst ratio is 0.5:1 to 10:1, or 1:1 to 5:1.

In at least one embodiment, the catalyst compounds can be combined with combinations of alumoxanes and NCA's as known in the art.

In at least one embodiment, when an NCA (such as an ionic or neutral stoichiometric activator) is used, the catalyst-to-activator molar ratio is typically from 1:10 to 1:1; 1:10 to 10:1; 1:10 to 2:1; 1:10 to 3:1; 1:10 to 5:1; 1:2 to 1.2:1; 1:2 to 10:1; 1:2 to 2:1; 1:2 to 3:1; 1:2 to 5:1; 1:3 to 1.2:1; 1:3 to 10:1; 1:3 to 2:1; 1:3 to 3:1; 1:3 to 5:1; 1:5 to 1:1; 1:5 to 10:1; 1:5 to 2:1; 1:5 to 3:1; 1:5 to 5:1; 1:1 to 1:1.2.

Likewise, a co-activator, such as a group 1, 2, or 13 organometallic species (e.g., an alkyl aluminum compound such as tri-n-octyl aluminum), may be used in the catalyst system herein. The catalyst-to-co-activator molar ratio is from 1:100 to 100:1; 1:75 to 75:1; 1:50 to 50:1; 1:25 to 25:1; 1:15 to 15:1; 1:10 to 10:1; 1:5 to 5:1; 1:2 to 2:1; 1:100 to 1:1; 1:75 to 1:1; 1:50 to 1:1; 1:25 to 1:1; 1:15 to 1:1; 1:10 to 1:1; 1:5 to 1:1; 1:2 to 1:1; 1:10 to 2:1.

Support Materials

In any of the embodiments herein, the catalyst system may comprise an inert support material. In at least one embodiment, the supported material is a porous support material, for example, talc, or inorganic oxides. Other support materials include zeolites, clays, organoclays, or any other suitable organic or inorganic support material and the like, or mixtures thereof.

In at least one embodiment, the support material is an inorganic oxide. Suitable inorganic oxide materials for use in metallocene catalyst systems herein include Groups 2, 4, 13, and 14 metal oxides, such as silica, alumina, and mixtures thereof. Other inorganic oxides that may be employed either alone or in combination with the silica, or alumina are magnesia, titania, zirconia, and the like. Other suitable support materials, however, can be employed, for example, functionalized polyolefins, such as polyethylene. Supports include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays, and the like. Also, combinations of these support materials may be used, for example, silica-chromium, silica-alumina, silica-titania, and the like. Support materials include SiO₂, Al₂O₃, ZrO₂, SiO₂, and combinations thereof.

The support material, such as an inorganic oxide, can have a surface area in the range of from about 10 to about 700 m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g and average particle size in the range of from about 5 to about 500 m. In at least one embodiment, the surface area of the support material is in the range of from about 50 to about 500 m²/g, pore volume of from about 0.5 to about 3.5 cc/g and average particle size of from about 10 to about 200 m. In at least one embodiment, the surface area of the support material is in the range is from about 100 to about 400 m²/g, pore volume from about 0.8 to about 3.0 cc/g and average particle size is from about 5 to about 100 m. The average pore size of the support material useful in the present disclosure is in the range of from 10 to 1000 Å, such as 50 to about 500 Å, such as 75 to about 350 Å. In some embodiments, the support material is a high surface area, amorphous silica (surface area=300 m²/gm; pore volume of 1.65 cm³/gm). Silicas are marketed under the tradenames of Davison 952 or Davison 955 by the Davison Chemical Division of W.R. Grace and Company. In other embodiments DAVISON 948 can be used. A preferred support material is silica ES70, which is available from PQ Corporation.

The support material should be dry, that is, substantially free of absorbed water. Drying of the support material can be effected by heating or calcining at about 100° C. to about 1000° C., such as at least about 600° C. When the support material is silica, it is heated to at least 200° C., such as about 200° C. to about 850° C., such as at about 600° C.; and for a time of about 1 minute to about 100 hours, from about 12 hours to about 72 hours, or from about 24 hours to about 60 hours. The calcined support material should have at least some reactive hydroxyl (OH) groups to produce supported catalyst systems of the present disclosure. The calcined support material is then contacted with at least one polymerization catalyst comprising at least one metallocene compound and an activator.

The support material, having reactive surface groups, typically hydroxyl groups, is slurried in a non-polar solvent and the resulting slurry is contacted with a solution of a metallocene compound and an activator. In some embodiments, the slurry of the support material is first contacted with the activator for a period of time in the range of from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours. The solution of the metallocene compound is then contacted with the isolated support/activator. In some embodiments, the supported catalyst system is generated in situ. In at least one embodiment, the slurry of the support material is first contacted with the catalyst compound for a period of time in the range of from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours. The slurry of the supported metallocene compound is then contacted with the activator solution.

The mixture of the catalyst, activator and support is heated to about 0° C. to about 70° C., such as to about 23° C. to about 60° C., such as at room temperature. Contact times typically range from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.

Suitable non-polar solvents are materials in which all of the reactants used herein, e.g., the activator, and the catalyst compound, are at least partially soluble and which are liquid at room temperature. Non-limiting example non-polar solvents are alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, cycloalkanes, such as cyclohexane, aromatics, such as benzene, toluene, and ethylbenzene.

Polymerization Methods

In embodiments herein, the present disclosure relates to polymerization processes where monomer (such as ethylene), and optionally comonomer (such as 1-hexene), are contacted with a catalyst system comprising an activator and at least one catalyst compound, as described above. The catalyst compound and activator may be combined in any order, and are combined typically prior to contacting with the monomer.

In at least one embodiment, a polymerization method includes a) contacting one or more olefin monomers with a catalyst system comprising: i) an activator and ii) a catalyst compound of the present disclosure. The activator may be an alumoxane or a non-coordination anion activator. The one or more olefin monomers may be ethylene or a mixture of ethylene and one or more 1-olefins comonomers (also referred to as α-olefins or “alpha olefins”) such as 1-butene, 1-hexene, and 1-octane.

Monomers useful herein include substituted or unsubstituted C₂ to C₄₀ alpha olefins, such as C₂ to C₂₀ alpha olefins, such as C₂ to C₁₂ α-olefins, such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof. In at least one embodiment, the monomer comprises propylene and an optional comonomers comprising one or more ethylene or C₄ to C₄₀ olefins, such as C₄ to C₂₀ olefins, such as C₆ to C₁₂ olefins. The C₄ to C₄₀ olefin monomers may be linear, branched, or cyclic. The C₄ to C₄₀ cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups. In at least one embodiment, the monomer comprises ethylene and an optional comonomers comprising one or more C₃ to C₄₀ olefins, such as C₄ to C₂₀ olefins, such as C₆ to C₁₂ olefins. The C₃ to C₄₀ olefin monomers may be linear, branched, or cyclic. The C₃ to C₄₀ cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.

Exemplary C₂ to C₄₀ olefin monomers and optional comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof, such as hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and their respective homologs and derivatives, such as norbornene, norbornadiene, and dicyclopentadiene.

The polymerization method of the present disclosure can be carried out in any suitable manner. Any suitable suspension, homogeneous, bulk, solution, slurry, or gas phase polymerization process can be used. Such processes can be run in a batch, semi-batch, or continuous mode. Homogeneous polymerization processes and slurry processes can be performed. (A useful homogeneous polymerization process is one where at least 90 wt % of the product is soluble in the reaction media.) A bulk homogeneous process can be used. (A preferred bulk process is one where monomer concentration in all feeds to the reactor is 70 vol % or more.) Alternately, no solvent or diluent is present or added in the reaction medium, (except for the small amounts used as the carrier for the catalyst system or other additives, or amounts typically found with the monomer; e.g., propane in propylene). In at least one embodiment, the process is a slurry polymerization process. As used herein the term “slurry polymerization process” means a polymerization process where a supported catalyst is employed and monomers are polymerized on the supported catalyst particles. At least 95 wt % of polymer products derived from the supported catalyst are in granular form as solid particles (not dissolved in the diluent). Suitable diluents/solvents for polymerization include non-coordinating, inert liquids. Examples include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (Isopar™); perhalogenated hydrocarbons, such as perfluorinated C₄-C₁₀ alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene. Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In at least one embodiment, aliphatic hydrocarbon solvents are used as the solvent, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In at least one embodiment, the solvent is not aromatic, such that aromatics are present in the solvent at less than 1 wt %, such as less than 0.5 wt %, such as less than 0 wt % based upon the weight of the solvents.

In specific embodiments of the polymerization method disclosed herein, the method comprises contacting at least one olefin with any of the catalyst systems disclosed herein and obtaining a polyolefin. In still further embodiments, the method comprises contacting two or more different olefins with any of the catalyst systems disclosed herein and obtaining a polyolefin. Preferably, the aforementioned at least one olefin is ethylene. Preferably, the aforementioned two or more olefins are ethylene and 1-hexene. In any of the foregoing embodiments of the polymerization methods disclosed herein, the produced polyolefin has a PDI of about 3.0 to about 13.0, preferably about 4.0 to about 13.0, and more preferably about 6.0 to about 13.0. In any of the foregoing embodiments of the polymerization methods disclosed herein, the polyolefin is preferably linear low density polyethylene (LLDPE) and the method is carried out in a gas phase or slurry process.

Polymerizations can be performed at any temperature and/or pressure suitable to obtain the desired polymers, such as ethylene and or ethylene/1-olefin polymers. Typical temperatures and/or pressures include a temperature in the range of from about 0° C. to about 300° C., such as about 20° C. to about 200° C., such as about 35° C. to about 150° C., such as about 40° C. to about 120° C., such as about 45° C. to about 85° C.; and at a pressure in the range of from about 0.35 MPa to about 10 MPa, such as about 0.45 MPa to about 6 MPa, such as about 0.9 MPa to about 4 MPa. In a typical polymerization, the run time of the reaction is up to about 60 minutes, alternatively from about 5 to 250 minutes, alternatively from about 10 to 45 minutes. Although the polymerization temperature is not critical, in one embodiment the polymerization method disclosed herein may comprise heating the one or more olefin monomers and any of the catalyst systems disclosed herein to about 85° C. and forming an ethylene homopolymer or an ethylene/1-olefin copolymer, such as an ethylene/1-hexene copolymer.

In some embodiments of the polymerization methods disclosed herein, hydrogen is present in the polymerization reactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa), such as from 0.01 to 25 psig (0.07 to 172 kPa), such as 0.1 to 10 psig (0.7 to 70 kPa).

Other additives may also be used in the polymerization, as desired, such as one or more scavengers, promoters, modifiers, chain transfer agents (such as diethyl zinc), reducing agents, oxidizing agents, hydrogen, aluminum alkyls, or silanes.

Useful chain transfer agents are typically alkylalumoxanes or Group 12 or 13 metal alkyls, the latter which are represented by the formula AlR₃, ZnR₂ (where each R is, independently, a C₁-C₈ aliphatic radical, such as methyl, ethyl, propyl, butyl, phenyl, hexyl octyl or an isomer thereof) or a combination thereof, such as diethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof.

Polyolefin Products

The present disclosure also relates to compositions of matter produced by the methods described herein. In at least one embodiment, the methods described herein produce ethylene homopolymers or ethylene copolymers, such as ethylene/1-hexene copolymers, having PDI values of about 3.0 to about 13.0, preferably about 4.0 to about 13.0, and more preferably about 6.0 to about 13.0. In further such embodiments, the ethylene copolymers have from 0 to 25 mol % (such as from 0.5 to 20 mol %, such as from 1 to 15 mol %, such as from 3 to 10 mol %) of one or more C₃ to C₂₀ olefin comonomer (such as C₃ to C₁₂ alpha-olefin, such as propylene, butene, hexene, octene, decene, dodecene, such as propylene, butene, hexene, octene), or are copolymers of propylene such as copolymers of propylene having from 0 to 25 mol % (such as from 0.5 to 20 mol %, such as from 1 to 15 mol %, such as from 3 to 10 mol %) of one or more of C₂ or C₄ to C₂₀ olefin comonomer (such as ethylene or C₄ to C₁₂ alpha-olefin, such as butene, hexene, octene, decene, dodecene, such as ethylene, butene, hexene, octene).

In still further embodiments the ethylene copolymers disclosed herein are ethylene/1-hexene copolymers having from about 0.5 to about 11 wt %, or from about 1.0 to about 11 wt %, or from about 2.0 to about 11 wt %, or from about 4.0 to 11 wt %, or from about 5.0 to 11 wt % of incorporated 1-hexene.

In at least one embodiment, the polymer produced herein has a multimodal molecular weight distribution as determined by Gel Permeation Chromatography (GPC). By “unimodal” is meant that the GPC trace has one peak or inflection point. By “multimodal” is meant that the GPC trace has at least two peaks or inflection points. An inflection point is that point where the second derivative of the curve changes in sign (e.g., from negative to positive or vice versus).

In at least one embodiment, the polymer produced herein has a multimodal composition distribution as determined by Cross Fractionation Chromatography (CFC), as described below. By “unimodal” is meant that the CFC trace has one peak or inflection point. By “multimodal” is meant that the CFC trace has at least two peaks or inflection points. An inflection point is that point where the second derivative of the curve changes in sign (e.g., from negative to positive or vice versus).

In yet further embodiments, the polymers produced as described herein have a g′_(vis) value, as determined by GPC-4D (discussed below) of about 1.0, alternatively from about 0.98 to about 1, alternatively about 0.9 to about 1.10, alternatively about 0.95 to about 1.10, alternatively about 1.0 to about 1.05, alternatively about 1.03. In yet further embodiments, the polymer produced as described herein has no long chain branching (LCB). The GPC-4D data were obtained using the technique described in the experimental section below. In still other embodiments the polymers produced herein have a total unsaturation/1000 C greater than 0.4.

Alternately, the polymers produced as described herein have a g′_(vis) value, as determined by GPC-4D (discussed below) of about from about 0.69 to about 1.06.

In at least one embodiment, the polymer produced herein has a composition distribution breadth index (CDBI) of 50% or more, such as 60% or more, such as 70% or more. CDBI is a measure of the composition distribution of monomer within the polymer chains and is measured by the procedure described in PCT publication WO 93/03093, published Feb. 18, 1993, as well as in Wild et al, J. Poly. Sci., Poly. Phys. Ed., Vol. 20, p. 441 (1982) and U.S. Pat. No. 5,008,204, including that fractions having a weight average molecular weight (Mw) below 15,000 are ignored when determining CDBI.

Films and Molded Articles

Any of the foregoing polymers of the present disclosure, such as the foregoing ethylene/1-olefin copolymers or blends thereof, may be used in a variety of end-use applications. Such applications include, for example, mono- or multi-layer blown, mono- or multi-layer cast, extruded, and/or shrink films. These films may be formed by any number of well-known extrusion or coextrusion techniques, such as a blown bubble film processing technique, wherein the composition can be extruded in a molten state through an annular die and then expanded to form a uni-axial or biaxial orientation melt prior to being cooled to form a tubular, blown film, which can then be axially slit and unfolded to form a flat film. Films may be subsequently unoriented, uniaxially oriented, or biaxially oriented to the same or different extents. Typically, one or more of the layers of the film are oriented in the transverse and/or longitudinal directions to the same or different extents. The uniaxially orientation can be accomplished using typical cold drawing or hot drawing methods. Biaxial orientation can be accomplished using tenter frame equipment or a double bubble processes and may occur before or after the individual layers are brought together. For example, a polyethylene layer can be extrusion coated or laminated onto an oriented polyethylene layer or the two layers can be coextruded together into a film then oriented. Likewise, oriented polypropylene could be laminated to oriented polyethylene or oriented polyethylene could be coated onto polypropylene then optionally the combination could be oriented even further. Typically the films are oriented in the Machine Direction (MD) at a ratio of up to 15, preferably between 5 and 7, and in the Transverse Direction (TD) at a ratio of up to 15, preferably 7 to 9. However, in another embodiment the film is oriented to the same extent in both the MD and TD directions. The films may vary in thickness depending on the intended application; however, films of a thickness from 1 to 50 μm are usually suitable. Films intended for packaging are usually from 10 to 50 μm thick. The thickness of the sealing layer is typically 0.2 to 50 μm. There may be a sealing layer on both the inner and outer surfaces of the film or the sealing layer may be present on only the inner or the outer surface.

In another embodiment, one or more layers fo the film may be modified by corona treatment, electron beam irradiation, gamma irradiation, flame treatment, or microwave. In a preferred embodiment, one or both of the surface layers is modified by corona treatment.

Other applications include the fabrication of molded articles by injection or blow molding, such as for example, blow molded bottles for milk, detergent, or other liquids.

Thus, in at least one aspect the present disclosure provides a mono- or multi-layer blown, cast, extruded, or shrink film comprising any of the polyolefins, preferably a linear low density polyethylene, prepared according to any embodiments of the polymerization methods set forth herein. In another aspect the present disclosure provides an injection or blow molded article comprising any of the polyolefins prepared according to any embodiments of the polymerization methods set forth herein.

This invention further relates to:

1. A catalyst compound represented by Formula (I):

where M is a group 4 metal, R³ is a C₃-C₄₀ branched alkyl, wherein the branched alkyl group is branched at the α-position, R^(3′) is hydrogen, methyl, ethyl, or a group containing three or more carbon atoms having the formula —CH₂R′, where R′ is an alkyl, aryl, or silyl group; each of R², R⁴, R⁵, R⁶, R⁷, R^(2′), R^(4′), R^(5′), R^(6′), and R^(7′) is independently hydrogen or a C₁-C₄₀ substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, alkoxyl, halogen, or siloxyl, or one or more of R⁴ and R⁵, R⁵ and R⁶, R⁶ and R⁷, R^(4′) and R^(5′), R^(5′) and R^(6′), and R^(6′) and R^(7′) are joined to form a completely saturated, partially saturated, or aromatic ring, T is a bridging group, and each X is independently a halide or C₁-C₅₀ substituted or unsubstituted hydrocarbyl, hydride, amide, alkoxide, sulfide, phosphide, halide, or a combination thereof, or two of X are joined together to form a metallocycle ring, or two of X are joined to form a chelating ligand, a diene ligand, or an alkylidene. 2. The catalyst compound of paragraph 1, wherein R³ is a C₃-C₄₀ branched alkyl represented by Formula (II):

where each R^(z) and R^(x) is, independently, a C₁ to C₂₀ alkyl group and R^(y) is hydrogen or a C₁ to C₄ alkyl group, preferably a C₁ to C₂ alkyl group. 3. The catalyst compound of paragraph 1 or 2, wherein T is represented by the formula R⁸ ₂J or (R⁸)J₂, where each J is independently selected from C, Si, or Ge, and each R⁸ is independently hydrogen, halogen, a C₁ to C₄₀ hydrocarbyl or a C₁ to C₄₀ substituted hydrocarbyl group, and two R⁸ can form a cyclic structure including completely saturated, partially saturated, aromatic, or fused ring systems 4. The catalyst compound of any of paragraphs 1 to 3, wherein R^(y) is hydrogen. 5. The catalyst compound of any of paragraphs 1 to 4, wherein each R^(x), R^(y), and R^(z) is different from any other R^(x), R^(y), and R^(z) such that the catalyst compound has a chiral center on the α-carbon of R³. 6. The catalyst compound of paragraph 4, wherein R^(z) is n-propyl and R^(x) is methyl. 7. The catalyst compound of any of paragraphs 1 to 6, wherein one or more of R⁴ and R⁵, R⁵ and R⁶, R⁶ and R⁷, R^(4′) and R^(5′), R^(5′) and R^(6′), and R^(6′) and R^(7′) are joined to form a completely saturated, partially saturated, or aromatic ring. 8. The catalyst compound of paragraph 7, wherein R⁵ and R⁶ are joined to form a partially saturated 5-membered ring. 9. The catalyst compound of any of paragraphs 1 to 8, wherein R^(3′) is methyl. 10. The catalyst compound of paragraph 1, 2 or 3, wherein each of R², R⁴, R⁵, R⁶, R⁷, R^(2′), R^(4′), R^(5′), R^(6′), and R^(7′) is hydrogen. 11. The catalyst compound of paragraph 10, wherein R^(3′) is methyl. 12. The catalyst compound of any of paragraphs 1 to 11, wherein J is Si and R⁸ is a C₁ to C₄₀ hydrocarbyl or a C₁ to C₄₀ substituted hydrocarbyl group. 13. The catalyst compound of any of paragraphs 1 to 12, wherein each R⁸ is a methyl group. 14. The catalyst compound of any of paragraphs 1 to 13, wherein M is Zr. 15. The catalyst compound of any of paragraphs 1 to 14, wherein each X is a halide. 16. The catalyst compound of paragraph 15, wherein each X is chloride. 17. The catalyst compound of paragraph 1, wherein the catalyst compound represented by Formula (I) corresponds to any one of the following structures:

18. A catalyst system comprising an activator and the catalyst compound of any of paragraphs 1 to 17. 19. A catalyst system according to paragraph 18, wherein the catalyst system utilizes a single catalyst compound. 20. The catalyst system of paragraph 18 or 19, wherein the catalyst system comprises a support material. 21. The catalyst system of paragraph 20, wherein said support material is silica. 22. The catalyst system of any of paragraphs 18 to 21, wherein the activator comprises one or more of alumoxanes, aluminum alkyls, and ionizing activators. 23. A method of polymerizing olefins to produce at least one polyolefin composition, the method comprising contacting at least one olefin with the catalyst system of any of paragraphs 18 to 23 and obtaining a polyolefin. 24. A method of polymerizing olefins to produce at least one polyolefin composition, the method comprising contacting two or more different olefins with the catalyst system of any of paragraphs 18 to 23 and obtaining a polyolefin. 25. The method of paragraph 23 or 24, wherein said at least one olefin is ethylene. 26. The method of paragraph 24, wherein said two or more olefins are ethylene and 1-hexene. 27. The method of any of paragraphs 23 to 26, wherein said polyolefin has an Mw/Mn of about 3.0 to about 13.0. 28. The method according to paragraph 27, wherein said polyolefin has an Mw/Mn of about 4.0 to about 13.0. 29. The method according to paragraph 28, wherein said polyolefin has an Mw/Mn of about 6.0 to about 13.0. 30. The method of any of paragraphs 23 to 29, wherein said polyolefin is linear low density polyethylene. 31. The method of paragraph 23, wherein said polyolefin has total unsaturation/1000 C greater than 0.25. 32. The method of any of paragraphs 23 to 31, wherein said polyolefin has g′_(vis) of about 0.9 to about 1.10. 33. The method of any of paragraphs 23 to 32, wherein said polyolefin has g′_(vis) of from about 0.98 to 1.0. 34. The method of any of paragraphs 23 to 33, wherein said method is carried out in a gas phase or slurry process. 35. The method of any of paragraphs 23 to 34, wherein the polyolefin is linear low density polyethylene and is formed into a biaxially oriented film. 36. A biaxially oriented polyethylene film comprising the linear low density polyethylene produced by the method of any of paragraphs 23 to 35, wherein said polyolefin is linear low density polyethylene. 37. The method of any of paragraphs 23 to 36, wherein the polyolefin produced herein has a multimodal composition distribution.

EXPERIMENTAL

The experimental methods and analytical techniques utilized in Examples below are described in this section.

Chemical structures and isomers of catalyst compounds of the present disclosure were determined by ¹H NMR. ¹H NMR data are collected at 23° C. in a 5 mm probe using a 400 MHz Bruker spectrometer with deuterated methylene chloride or deuterated benzene. Data is recorded using a maximum pulse width of 45°, 8 seconds between pulses and signal averaging 16 transients. The spectrum is reported relative to residual protium in the deuterated benzene, which is referenced to 7.16 ppm.

Synthesis

Lithium Indenide:

To a precooled, stirring solution of indene (29.57 g, 0.255 mol) in hexane (500 mL), n-butyllithium (2.5 M in hexanes, 103 mL, 0.257 mol, 1.01 eq.) was added slowly. The reaction was stirred at room temperature for 23 h. The solid was collected by filtration and washed with hexane (50 mL). The solid was concentrated under high vacuum to afford the product as a white powder (29.984 g).

1-Methyl-1H-indene

To a precooled, stirring solution of iodomethane (4.206 g, 0.030 mol) in diethyl ether (60 mL), lithium indenide (1.235 g) was added in portions with diethyl ether (5 mL). The reaction was stirred at room temperature for 4 hours. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with hexane (20 mL) and filtered over Celite. The extract was concentrated under a stream of nitrogen and then under high vacuum. The residue was again extracted with hexane (10 mL) and filtered over Celite. The extract was concentrated under a stream of nitrogen and then under high vacuum to afford a mixture of oil and solid. The oil was filtered over Celite and concentrated under high vacuum to afford the product as a clear, colorless oil (0.397 g).

An alternative synthesis for 1-Methyl-1H-indene is as follows: To a precooled, stirring solution of iodomethane (3.476 g, 0.024 mol) in tetrahydrofuran (90 mL), a precooled solution of lithium indenide (2.389 g, 0.020 mol) in tetrahydrofuran (20 mL) was added. The reaction was stirred at room temperature for 16.5 hours. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with hexane (40 mL) and filtered over Celite. The extract was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted again with hexane (10 mL) and filtered over Celite. The extract was concentrated under a stream of nitrogen and then under high vacuum to afford a mixture of oil and solid. The oil was separated from the solid by pipette to afford the product as a clear, colorless oil (0.972 g, mixture of isomers).

Lithium 1-methyl-1H-inden-1-ide:

To a precooled, stirring solution of 1-methyl-1H-indene (1.637 g, 0.012 mol) in hexane (20 mL), n-butyllithium (2.5 M in hexanes, 4.9 mL, 0.012 mol, 1.05 eq.) was added. The reaction was stirred at room temperature for 2.5 hours. The reaction was filtered, and the solid was concentrated under high vacuum to afford the product as a white solid, containing diethyl ether (0.01 eq.) and hexane (0.18 eq.) (1.622 g).

3-(pentan-2-yl)-1H-indene

To a stirring solution of lithium indenide (2.851 g, 0.023 mol) in tetrahydrofuran (90 mL), 2-bromopentane (3.1 mL, 0.024 mol) was added. The reaction was stirred and heated to 60° C. for 16 hours. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with hexane and filtered over Celite. The hexane extract was concentrated under a stream of nitrogen and then under high vacuum to give the crude as an oil. The oil was purified over silica gel (Biotage, 100 g column), eluting with hexane to afford the product as a clear colorless oil (3.355 g, mixture of isomers).

An alternative synthesis of 3-(pentan-2-yl)-1H-indene is as follows: To a stirring solution of lithium indenide (1.313 g, 0.011 mol) in tetrahydrofuran (40 mL), 2-bromopentane (1.4 mL, 0.011 mol) was added. The reaction was stirred and heated to 60° C. for 2 hours. Volatiles were removed under high vacuum. The residue was extracted with hexane (20 mL) and filtered over Celite. The extract was concentrated under a stream of nitrogen and then under high vacuum. The resulting oil was purified over silica (Biotage, 25 g column), eluting with hexane, to afford the product (1.454 g).

Lithium 1-(pentan-2-yl)-1H-inden-1-ide:

To a precooled, stirring solution of 3-(pentan-2-yl)-1H-indene (1.036 g, 0.006 mol, mixture of isomers) in diethyl ether (40 mL), n-butyllithium (2.5 M in hexane, 2.3 mL, 0.006 mol) was added. The reaction was stirred at room temperature for 50 minutes. Volatiles were removed under a stream of nitrogen and then under high vacuum to afford the product as a white, foam-like solid containing residual diethyl ether (0.13 eq.) (1.115 g).

An alternative synthesis of lithium 1-(pentan-2-yl)-1H-inden-1-ide is as follows: To a precooled, stirring solution of 3-(pentan-2-yl)-1H-indene (1.454 g, 0.008 mol) in diethyl ether (20 mL), n-butyllithium (2.5 M in hexane) was added. The reaction was stirred at room temperature for 1 hour. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with hexane (20 mL) and filtered over Celite. The extract was concentrated under high vacuum. The extract was again extracted with hexane (10 mL) and filtered over Celite. The extract was concentrated under high vacuum to afford the product as an off-white solid (0.922 g).

1-Chloro-1,1,2,2-tetramethyl-2-(3-(pentan-2-yl)-1H-inden-1-yl)disilane

To a precooled, stirring solution of 1,2-dichloro-1,1,2,2-tetramethyldisilane (0.518 g, 0.003 mol) in diethyl ether (40 mL), a solution of lithium 1-(pentan-2-yl)-1H-inden-1-ide (0.558 g, 0.003 mol) in diethyl ether (10 mL) was added slowly over 2 minutes. The reaction was stirred at room temperature for 5.5 hours. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with hexane (15 mL) and filtered over Celite. The extract was concentrated under a stream of nitrogen and then under high vacuum to afford the product as a clear, colorless oil (0.852 g).

1,1,2,2-Tetramethyl-1-(3-methyl-1H-inden-1-yl)-2-(3-(pentan-2-yl)-1H-inden-1-yl)disilane

To a precooled, stirring solution of lithium 1-methyl-1H-indenide (0.191 g, 0.001 mol) in diethyl ether (40 mL), 1-chloro-1,1,2,2-tetramethyl-2-(3-(pentan-2-yl)-1H-inden-1-yl)disilane (0.465 g, 0.001 mol) with diethyl ether (5 mL) was added. The reaction was stirred at room temperature for 82 minutes. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with hexane (30 mL) and filtered over Celite. The extract was concentrated under a stream of nitrogen and then under high vacuum to afford the product as a clear, colorless oil (0.586 g).

Lithium 3-methyl-1-(1,1,2,2-tetramethyl-2-(3-(pentan-2-yl)-1H-inden-1-id-1-yl)disilanyl)-1H-inden-1-ide

To a precooled, stirring solution of 1,1,2,2-tetramethyl-1-(3-methyl-1H-inden-1-yl)-2-(3-(pentan-2-yl)-1H-inden-1-yl)disilane (0.568 g, 0.001 mol) in diethyl ether (30 mL), n-butyllithium (2.5 M solution in hexane, 1.1 mL, 0.003 mol) was added. The reaction was stirred at room temperature for 54 minutes. Volatiles were removed under a stream of nitrogen and then under high vacuum to afford the product as a white powder, containing diethyl ether (0.45 eq.) (0.679 g).

Tetramethyldisilylene(3-methyl-indenyl)(3-(2-pentanyl)-indenyl)zirconium(IV) dichloride

To a precooled, stirring suspension of zirconium(IV) chloride (0.285 g, 0.001 mol) in diethyl ether (30 mL), a solution of lithium 3-methyl-1-(1,1,2,2-tetramethyl-2-(3-(pentan-2-yl)-1H-inden-1-id-1-yl)disilanyl)-1H-inden-1-ide (0.541 g, 0.001 mol) in diethyl ether (30 mL) was added. The reaction was stirred at room temperature for 15.5 hours. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane (10 mL and 5 mL) and filtered over Celite. The combined extracts were concentrated under a stream of nitrogen and then under high vacuum. The extract was crystallized in pentane by slow evaporation and washed with minimal pentane to afford the product as yellow crystals (0.037 g, 5%, 1.0:1.3:2.4:3.9 ratio of diastereomers A, B, C, and D); indicative ¹H NMR (400 MHz, CD₂Cl₂): δ 6.61 (s, 1H, isomer C, used for isomer ratio), 6.57 (s, 1H, isomer B, used for isomer ratio), 6.56 (s, 1H, isomer B), 6.54 (s, 1H, isomer C), 6.37 (s, 1H, isomer D, used for isomer ratio), 6.34 (s, 1H, isomer A, used for isomer ratio), 6.26 (s, 1H isomer A, 1H isomer D).

Chlorodimethyl(3-(pentan-2-yl)-1H-inden-1-yl)silane

To a precooled, stirring solution of dichlorodimethylsilane (5.342 g, 0.041 mol, 15 eq.) in diethyl ether (80 mL), lithium 1-(pentan-2-yl)-1H-inden-1-ide (0.557 g, 0.003 mol) in diethyl ether (10 mL) was added. The reaction was stirred at room temperature for 5.5h. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with hexane (15 mL) and filtered over Celite. The hexane extract was concentrated under a stream of nitrogen and then under high vacuum to afford the product as a clear, colorless oil, containing hexane (0.10 eq.) (0.791 g).

Dimethyl(3-(pentan-2-yl)-1H-inden-1-yl)silyl trifluoromethanesulfonate

To a stirring suspension of silver(I) trifluoromethanesulfonate (0.685 g, 0.003 mol, 1 eq.) in toluene (20 mL), a solution of chlorodimethyl(3-(pentan-2-yl)-1H-inden-1-yl)silane (0.791 g, 0.003 mol) in toluene (5 mL) was added. The reaction was stirred at room temperature for 20 minutes. The reaction was filtered over Celite, and the filtered solid was further extracted with toluene (5 mL). The combined toluene extracts were concentrated under high vacuum to afford the product as a brown oil, containing toluene (1 eq.) (1.101 g).

Dimethyl(3-methyl-1H-inden-1-yl)(3-(pentan-2-yl)-1H-inden-1-yl)silane

To a stirring solution of lithium 1-methyl-1H-indenide (0.212, 0.001 mol, 1.04 eq.) in diethyl ether (20 mL), dimethyl(3-(pentan-2-yl)-1H-inden-1-yl)silyl trifluoromethanesulfonate (0.690 g, 0.001 mol) with diethyl ether (10 mL) was added. The reaction stirred at room temperature for 5 minutes. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with hexane (40 mL) and filtered over Celite. The hexane extract was concentrated under a stream of nitrogen and then under high vacuum to afford the product as a yellow oil (0.526 g).

Lithium 1-(dimethyl(3-methyl-1H-inden-1-yl)silyl)-3-(pentan-2-yl)-1H-inden-1-ide

To a precooled, stirring solution of dimethyl(3-methyl-1H-inden-1-yl)(3-(pentan-2-yl)-1H-inden-1-yl)silane (0.526 g, 0.001 mol) in diethyl ether (40 mL), n-butyllithium (2.5 M in hexanes, 1.129 mL, 0.003 mol, 2 eq.) was added. The reaction was stirred at room temperature for 20 minutes. Volatiles were removed under a stream of nitrogen and then under high vacuum to afford the product, containing diethyl ether (1.49 eq.) (0.683 g).

Dimethylsilyl (3-methyl-indenyl) (3-(2-pentanyl)-indenyl)zirconium(IV) dichloride

To a precooled, stirring suspension of zirconium(IV) chloride (0.317 g, 0.001 mol) in diethyl ether (40 mL), a solution of lithium 1-(dimethyl(3-methyl-1H-inden-1-yl)silyl)-3-(pentan-2-yl)-1H-inden-1-ide (0.683 g, 0.001 mol, 1.02 eq.) in diethyl ether (50 mL) was added. The reaction was stirred at room temperature for 4 hours. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane (2×20 mL) and filtered over Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum. The dichloromethane extract was washed with hexane and pentane to afford the product as an orange solid, of which some was removed for use in supportation (0.082 g, 11%, as a 1:1.7:2.3:3 ratio of diastereomers A, B, C, and D). The remaining portion of the hexane and pentane washed dichloromethane extract was extracted with toluene and concentrated under high vacuum. The toluene extract was washed with cold (−35° C.) pentane and concentrated under high vacuum to afford another fraction of the product as an orange solid (0.111 g, 15%, as a 1:3.3:2.3:7.3 ratio of diastereomers A, B, C, and D). ¹H NMR (400 MHz, CD₂Cl₂): δ 7.62-6.89 (m, 32H), 5.98 (s, 1H, isomer B, used for isomer ratio), 5.92 (s, 1H, isomer A, used for isomer ratio), 5.85 (s, 1H), 5.84 (s, 1H), 5.83 (s, 1H, isomer D, used for isomer ratio), 5.74 (s, 1H), 5.73 (s, 1H, isomer C, used for isomer ratio), 5.71 (s, 1H), 3.33-3.22 (m, 1H), 3.22-3.12 (m, 1H), 3.12-3.03 (m, 1H), 3.02-2.92 (m, 1H), 2.40 (d, 1H, J=0.6 Hz), 2.38 (d, 1H, J=0.5 Hz), 2.32 (d, 1H, J=0.6 Hz), 2.28 (d, 1H, J=0.6 Hz), 1.79-0.77 (m, 64H).

3-(1-phenylethyl)-1H-indene

To a precooled, stirring solution of lithium indenide (2.087 g, 0.017 mol) in tetrahydrofuran (30 mL), a solution of (1-bromoethyl)benzene (3.163 g, 0.017 mol) in tetrahydrofuran (10 mL) was added. The reaction was stirred and heated to 58° C. for 16 hours. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (15 mL) and filtered over Celite. The pentane extract was concentrated under a stream of nitrogen and then under high vacuum to afford the product, containing residual tetrahydrofuran (0.15 eq.) (2.678 g, mixture of isomers).

Lithium 1-(1-phenylethyl)-1H-inden-1-ide

To a precooled, stirring solution of 3-(1-phenylethyl)-1H-indene (0.835 g, 0.004 mol, mixture of isomers) in diethyl ether (30 mL), n-butyllithium (2.5 M in hexane, 1.5 mL, 0.004 mol) was added. The reaction was stirred at room temperature for 30 minutes. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was washed with pentane and concentrated under high vacuum to afford the product containing residual diethyl ether (0.10 eq.) and pentane (0.15 eq.) (0.902 g).

Dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silyl trifluoromethanesulfonate

To a precooled, stirring solution of silver(I) trifluoromethanesulfonate (0.610 g, 0.002 mol, 1.01 eq.) in toluene (15 mL), chlorodimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane (0.505 g, 0.002 mol) was added with toluene (5 mL). The reaction was stirred at room temperature for 65 minutes. The reaction was filtered over Celite. The filtrate was concentrated under high vacuum at 40° C. to afford the product as a clear, colorless oil (0.531 g).

Dimethyl(3-(1-phenylethyl)-1H-inden-1-yl)(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane

To a precooled, stirring solution of dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silyl trifluoromethanesulfonate (0.531 g, 0.002 mol) in diethyl ether (15 mL), lithium 1-(1-phenylethyl)-1H-inden-1-ide (0.441 g, 0.002 mol, 1.21 eq.) was added with diethyl ether (10 mL). The reaction was stirred at room temperature for 29 minutes. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (10 mL, then 20 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to afford the product as an orange oil, containing pentane (0.19 eq.) (0.688 g).

Lithium 1-(dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-ide-1-yl)silyl)-3-(1-phenylethyl)-1H-inden-1-ide

To a precooled, stirring solution of dimethyl(3-(1-phenylethyl)-1H-inden-1-yl)(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane (0.688 g, 0.002 mol) in diethyl ether (30 mL), n-butyllithium (2.5 M in hexanes, 1.4 mL, 0.004 mol, 2.1 eq.) was added. The reaction was stirred at room temperature for 100 minutes. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was washed with pentane (10 mL) and concentrated under high vacuum to afford the product as a white powder, containing diethyl ether (1.49 eq.) and pentane (0.56 eq.) (0.692 g).

Dimethylsilyl (3-(1-phenylethyl)-indenyl) (tetramethylcyclopentadienyl) zirconium(IV) dichloride

To a precooled, stirring suspension of lithium 1-(dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-ide-1-yl)silyl)-3-(1-phenylethyl)-1H-inden-1-ide (0.692 g, 0.001 mol) in diethyl ether (30 mL), zirconium(IV) chloride (0.287 g, 0.001 mol, 1 eq.) was added with diethyl ether (10 mL). The reaction was stirred at room temperature for 19 hours. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane (15 mL) and filtered over Celite. The extract was concentrated under a stream of nitrogen and then under high vacuum to give a yellow-orange foam. The foam was washed with pentane (2×10 mL) and concentrated under high vacuum to afford the product as a yellow powder (0.412 g, 59%, as a 1:1.9 ratio of diastereomers A and B). ¹H NMR (400 MHz, CD₂Cl₂): δ 7.97 (dt, 1H, J=8.8, 1.0 Hz, A), 7.50 (dt, 1H, J=8.7, 1.1 Hz, A), 7.41 (dt, 1H, J=8.7, 1.0 Hz, B), 7.34 (ddd, 1H, J=8.8, 6.7, 1.0 Hz, A), 7.28-7.01 (m, 6H from A, 7H from B), 6.95 (ddd, 1H, J=8.6, 6.3, 1.5 Hz, B), 5.98 (s, 1H, isomer B, used for isomer ratio), 5.47 (s, 1H, isomer A, used for isomer ratio), 4.60 (q, 1H, J=7.3 Hz, A), 4.53 (q, 1H, J=6.9 Hz, B), 1.99 (s, 3H, B), 1.97 (s, 3H, B), 1.96 (s, 3H, A), 1.94 (s, 3H, B), 1.93 (s, 3H, A), 1.92 (s, 3H, B), 1.90 (s, 3H, A), 1.89 (d, 3H, J=7.3 Hz, A), 1.72 (s, 3H, A), 1.52 (d, 3H, J=6.9 Hz, B), 1.18 (s, 3H, B), 1.12 (s, 3H, A), 1.05 (s, 3H, B), 0.83 (s, 3H, A).

Lithium 1,5,6,7-tetrahydro-s-indacen-1-ide

To a precooled, stirring solution of 1,2,3,5-tetrahydro-s-indacene (2.598 g, 0.017 mol) in diethyl ether (20 mL), n-butyllithium (2.5 M in hexanes, 6.7 mL, 0.017 mol, 1.01 eq.) was added. The reaction was stirred at room temperature for 15 minutes. The reaction was filtered on a fritted funnel. The filtered solid was washed with diethyl ether (2×5 mL) and concentrated under high vacuum to afford the product as a white solid, containing diethyl ether (0.85 eq.) and hexane (0.31 eq.) (3.894 g).

7-(Pentan-2-yl)-1,2,3,5-tetrahydro-s-indacene

To a precooled, stirring solution of 2-bromopentane (0.9 mL, 0.007 mol, 1.06 eq.) in tetrahydrofuran, a solution of lithium 1,5,6,7-tetrahydro-s-indacen-1-ide in tetrahydrofuran (total of 40 mL in the reaction) was added. The reaction was stirred and heated to 60° C. for 16 hours. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (2×10 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to give a yellow oil. The oil was purified via silica gel chromatography using a hexane eluent to afford the product as a clear liquid, containing hexane (0.38 eq.) (1.299 g).

Chlorodimethyl(3-(pentan-2-yl)-1,5,6,7-tetrahydro-s-indacen-1-yl)silane

To a stirring solution of dichlorodimethylsilane (5.0 mL, 0.041 mol, 14.9 eq.) in diethyl ether (60 mL), a solution of lithium 1-(pentan-2-yl)-1,5,6,7-tetrahydro-s-indacen-1-ide (0.643 g, 0.003 mol) in diethyl ether (40 mL) was added. The reaction was stirred at room temperature for 90 minutes. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (2×20 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to afford the product as a clear, colorless oil, containing diethyl ether (0.01 eq.) (0.599 g).

Dimethyl(3-(pentan-2-yl)-1,5,6,7-tetrahydro-s-indacen-1-yl)silyl trifluoromethanesulfonate

To a precooled, stirring solution of chlorodimethyl(3-(pentan-2-yl)-1,5,6,7-tetrahydro-s-indacen-1-yl)silane (0.599 g, 0.002 mol) in toluene (15 mL), silver(I) trifluoromethanesulfonate (0.481 g, 0.002 mol, 1 eq.) was added with toluene (10 mL). The reaction was stirred at room temperature for 10 minutes. The reaction was filtered over Celite. The filtrate was concentrated under high vacuum at 45° C. to afford the product as a dark oil (0.674 g).

Dimethyl(3-methyl-1H-inden-1-yl)(3-(pentan-2-yl)-1,5,6,7-tetrahydro-s-indacen-1-yl)silane

To a stirring solution of dimethyl(3-(pentan-2-yl)-1,5,6,7-tetrahydro-s-indacen-1-yl)silyl trifluoromethanesulfonate (0.674 g, 0.002 mol) in diethyl ether (20 mL), lithium 1-methyl-1H-indenide (0.240 g, 0.002 mol, 1.03 eq.) was added. The reaction was stirred at room temperature for 16 hours. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (20 mL) and filtered over Celite. The pentane extract was concentrated under a stream of nitrogen and then under high vacuum to afford the product as a yellow oil (0.545 g).

Lithium 1-(dimethyl(3-methyl-1H-inden-1-id-1-yl)silyl)-3-(pentan-2-yl)-1,5,6,7-tetrahydro-s-indacen-1-ide

To a precooled, stirring solution of dimethyl(3-methyl-1H-inden-1-yl)(3-(pentan-2-yl)-1,5,6,7-tetrahydro-s-indacen-1-yl)silane (0.545 g, 0.001 mol) in diethyl ether (20 mL), n-butyllithium (2.5 M in hexanes, 1.1 mL, 0.003 mol, 2.08 eq.) was added. The reaction was stirred at room temperature for 53 minutes. Volatiles were removed under a stream of nitrogen and then under high vacuum to afford the product as a yellow foam, containing diethyl ether (1.09 eq.) and hexane (1.05 eq.) (0.627 g).

Dimethylsilyl (3-methyl-indenyl) (3-(2-pentanyl)-1,5,6,7-tetrahydro-s-indacenyl) zirconium(IV) dichloride

To a precooled, stirring suspension of zirconium(IV) chloride (0.235 g, 0.001 mol) in diethyl ether (20 mL), a solution of lithium 1-(dimethyl(3-methyl-1H-inden-1-id-1-yl)silyl)-3-(pentan-2-yl)-1,5,6,7-tetrahydro-s-indacen-1-ide (0.627 g, 0.001 mol, 1.04 eq.) in diethyl ether (20 mL) was added. The reaction was stirred at room temperature for 70 minutes. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane and filtered over Celite. The extract was concentrated under a stream of nitrogen and then under high vacuum to give a red oil. Pentane (5 mL) was added to the oil, and the mixture was stirred until the precipitation of orange solid was complete. The solid was isolated and washed with more pentane (3×5 mL). The pentane washed dichloromethane extract was concentrated under high vacuum to afford the product as an orange solid (0.182 g, 31%, 1:2.8:3.3:5.1 ratio of diastereomers A, B, C, and D). ¹H NMR (400 MHz, CD₂Cl₂): δ7.59-6.88 (m, 24H), 5.90 (s, 1H), 5.84 (s, 2H), 5.83 (s, 1H), 5.74 (s, 1H), 5.72 (s, 1H), 5.70 (s, 1H), 5.65 (s, 1H), 3.27-2.65 (m, 20H), 2.38 (d, 3H, J=0.6 Hz, isomer B, used for isomer ratio), 2.36 (d, 3H, J=0.5 Hz, isomer D, used for isomer ratio), 2.32 (d, 3H, J=0.6 Hz, isomer C, used for isomer ratio), 2.30 (d, 3H, J=0.6 Hz, isomer A, used for isomer ratio), 2.14-1.89 (m, 8H), 1.78-0.76 (m, 40H), 1.31 (s, 3H), 1.28 (s, 3H), 1.13 (s, 3H), 1.10 (s, 3H), 1.04 (s, 3H), 1.03 (s, 3H), 0.93 (s, 3H), 0.89 (s, 3H).

(1H-Inden-1-yl)dimethyl(3-(pentan-2-yl)-1H-inden-1-yl)silane

To a stirring solution of dimethyl(3-(pentan-2-yl)-1H-inden-1-yl)silyl trifluoromethanesulfonate (1.003 g, 0.003 mol) in diethyl ether (40 mL), lithium indenide (0.312 g, 0.003 mol, 1 eq.) was added with diethyl ether (10 mL). The reaction was stirred at room temperature for 2.5 days. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (2×20 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to afford the product, containing pentane (0.31 eq.) (0.998 g).

Lithium 1-(2-(1H-inden-1-id-1-yl)-1,1,2,2-tetramethyldisilanyl)-3-(pentan-2-yl)-1H-inden-1-ide

To a precooled, stirring solution of (1H-inden-1-yl)dimethyl(3-(pentan-2-yl)-1H-inden-1-yl)silane (0.998 g, 0.003 mol) in diethyl ether (30 mL), n-butyllithium (2.5 M in hexanes, 2.15 mL, 0.005 mol, 2.03 eq.) was added. The reaction was stirred at room temperature for 35 minutes. Volatiles were removed under a stream of nitrogen and then under high vacuum to give a white foam. The foam was washed with pentane (20 mL) and concentrated under high vacuum to afford the product as a white powder, containing diethyl ether (0.81 eq.) and pentane (1.09 eq.) (1.117 g).

Dimethylsilyl (3-(2-pentanyl)-indenyl) (indenyl) zirconium(IV) dichloride

To a precooled, stirring suspension of zirconium(IV) chloride (0.542 g, 0.002 mol) in diethyl ether (40 mL), a solution of lithium 1-(2-(1H-inden-1-id-1-yl)-1,1,2,2-tetramethyldisilanyl)-3-(pentan-2-yl)-1H-inden-1-ide (1.117 g, 0.002 mol, 1.02 eq.) in diethyl ether (20 mL) was added. The reaction was stirred at room temperature for 16h. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane (2×20 mL) and filtered over Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum to give an orange-red foam. The foam was washed with pentane (20 mL, then 30 mL) and then concentrated under high vacuum. The foam was then extracted with diethyl ether (2×5 mL). The combined diethyl ether extracts were cooled to −35° C. The precipitate from cold diethyl ether was collected and concentrated under high vacuum to afford the product as an orange solid (0.055 g, 4%, 1:2.7:2.9:2.9 ratio of diastereomers A, B, C, and D). ¹H NMR (400 MHz, CD₂Cl₂): δ 7.65-6.87 (m, 34H), 6.80 (dd, 1H, J=3.3, 0.9 Hz), 6.78 (dd, 1H, J=3.3, 1.0 Hz), 6.20 (d, 1H, J=3.3 Hz, isomer C, used for isomer ratio), 6.17 (d, 1H, J=3.2 Hz, isomer D, used for isomer ratio), 6.15 (d, 1H, J=3.3 Hz, isomer A, used for isomer ratio), 6.10 (d, 1H, J=3.2 Hz, isomer B, used for isomer ratio), 5.97 (s, 1H), 5.93 (s, 1H), 5.92 (s, 1H), 5.81 (s, 1H), 3.23-2.91 (m, 4H), 1.70-0.77 (m, 64H).

(1H-Inden-1-yl)dimethyl(3-(pentan-2-yl)-3,5,6,7-tetrahydro-s-indacen-1-yl)silane

To a stirring solution of dimethyl(3-(pentan-2-yl)-1,5,6,7-tetrahydro-s-indacen-1-yl)silyl trifluoromethanesulfonate (1.932 g, 0.004 mol) in diethyl ether (30 mL), lithium indenide (0.545 g, 0.004 mol, 1 eq.) was added with diethyl ether (20 mL). The reaction was stirred at room temperature for 54 minutes Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane and then filtered over Celite. The extract was concentrated under a stream of nitrogen and then under high vacuum to afford the product as an oil (1.829 g).

Lithium 1-((1H-inden-1-id-1-yl)dimethylsilyl)-3-(pentan-2-yl)-1,5,6,7-tetrahydro-s-indacen-1-ide

To a stirring solution of (1H-inden-1-yl)dimethyl(3-(pentan-2-yl)-3,5,6,7-tetrahydro-s-indacen-1-yl)silane (1.829 g, 0.005 mol) in diethyl ether (30 mL), n-butyllithium (2.5 M in hexanes, 3.7 mL, 0.009 mol, 2.02 eq.) was added. The reaction was stirred at room temperature for 57 minutes. Volatiles were removed under a stream of nitrogen and then under high vacuum to afford the product as an off-white powder, containing diethyl ether (0.53 eq.) (1.881 g).

Dimethylsilyl (3-(2-pentanyl)-1,5,6,7-tetrahydro-s-indacenyl) indenyl zirconium(IV) dichloride

To a precooled, stirring solution of lithium 1-((1H-inden-1-id-1-yl)dimethylsilyl)-3-(pentan-2-yl)-1,5,6,7-tetrahydro-s-indacen-1-ide (1.881 g, 0.004 mol) in diethyl ether (30 mL), zirconium(IV) chloride (0.975 g, 0.004 mol, 1 eq.) was added. The reaction was stirred at room temperature for 3h. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane (2×20 mL) and filtered over Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum. The extract was washed with pentane (2×10 mL) and hexane (20 mL) to afford the product as an orange powder (1.544 g, 66%, 1:1.1:1.2:1.2 ratio of diastereomers A, B, C, and D).). ¹H NMR (400 MHz, CD₂Cl₂): δ 7.64-6.90 (m, 26H), 6.78 (dd, 1H, J=3.3, 0.9 Hz), 6.76 (dd, 1H, J=3.2, 1.0 Hz), 6.17 (d, 1H, J=3.3 Hz), 6.14 (d, 1H, J=3.3 Hz), 6.14 (d, 1H, J=3.3 Hz), 6.08 (d, 1H, J=3.2 Hz), 5.88 (s, 1H, isomer C, used for isomer ratio), 5.84 (s, 1H, isomer B, used for isomer ratio), 5.83 (s, 1H, isomer A, used for isomer ratio), 5.73 (s, 1H, isomer D, used for isomer ratio), 3.20-2.63 (m, 20H), 2.12-1.90 (m, 8H), 1.76-0.77 (m, 64H).

Dimethyl(3-(pentan-2-yl)-1H-inden-1-yl)(1,5,6,7-tetrahydro-s-indacen-1-yl)silane

To a stirring solution of dimethyl(3-(pentan-2-yl)-1H-inden-1-yl)silyl trifluoromethanesulfonate (0.475 g, 0.001 mol) in diethyl ether (20 mL), lithium 1,5,6,7-tetrahydro-s-indacen-1-ide (0.297 g, 0.001 mol, 1 eq.) was added with diethyl ether (10 mL). The reaction was stirred at room temperature for 18 hours. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (15 mL) and filtered over Celite. The pentane extract was concentrated under a stream of nitrogen and then under high vacuum to afford the product as a red-orange oil (0.408 g).

Lithium 1-(dimethyl(3-(pentan-2-yl)-1H-inden-1-id-1-yl)silyl)-1,5,6,7-tetrahydro-s-indacen-1-ide

To a precooled, stirring solution of dimethyl(3-(pentan-2-yl)-1H-inden-1-yl)(1,5,6,7-tetrahydro-s-indacen-1-yl)silane (0.408 g, 0.001 mol) in diethyl ether (20 mL), n-butyllithium (2.5 M in hexanes, 0.82 mL, 0.002 mol, 2 eq.) was added. The reaction was stirred at room temperature for 2.5 hours. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was washed with hexane and concentrated under high vacuum to afford the product as an orange solid, containing diethyl ether (0.57 eq.) (0.367 g).

Dimethylsilyl (3-(2-pentanyl)-indenyl) (1,5,6,7-tetrahydro-s-indacenyl) zirconium(IV) dichloride

To a precooled, stirring solution of lithium 1-(dimethyl(3-(pentan-2-yl)-1H-inden-1-id-1-yl)silyl)-1,5,6,7-tetrahydro-s-indacen-1-ide (0.367 g, 0.81 mmol) in diethyl ether (40 mL), zirconium(IV) chloride (0.190 g, 0.82 mmol, 1.01 eq.) was added. The reaction was stirred at room temperature for 2.5 hours. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane (15 mL) and filtered over Celite. The extract was concentrated under a stream of nitrogen and then under high vacuum. The dichloromethane extract was extracted with pentane (2×10 mL). The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum. The pentane extracts were redissolved in minimal pentane (2 mL) and cooled to −35° C. The precipitate was collected and concentrated under high vacuum to afford the product as a red-orange solid (0.132 g, 29%, 1:1:1:1 ratio of diastereomers A, B, C, and D). ¹H NMR (400 MHz, CD₂Cl₂): δ 7.57-6.86 (m, 24H), 6.86-6.84 (m, 1H), 6.83 (d, 1H, J=2.7 Hz), 6.67 (d, 1H, J=3.1 Hz), 6.65 (d, 1H, J=3.0 Hz), 6.10 (d, 1H, J=3.4 Hz), 6.09 (d, 1H, J=3.3 Hz), 6.06 (d, 1H, J=3.3 Hz), 6.01 (s, 1H, isomer A, used for isomer ratio), 6.00 (d, 1H, J=3.2 Hz), 5.94 (s, 1H, isomer B, used for isomer ratio), 5.92 (s, 1H, isomer C, used for isomer ratio), 5.80 (s, 1H, isomer D, used for isomer ratio), 3.22-2.67 (m, 20H), 2.14-1.88 (m, 8H), 1.76-0.75 (m, 64H).

Lithium 1H-cyclopenta[a]naphthalen-1-ide

To a stirring solution of 1H-cyclopenta[a]naphthalene (3.038 g, 0.018 g) in diethyl ether (40 mL), n-butyllithium (2.5 M in hexanes, 7.4 mL, 0.019 mol, 1.01 eq.) was added. The reaction was stirred at room temperature for 55 minutes. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was washed with hexane (10 mL) and filtered. The filtered solid was collected and concentrated under high vacuum to afford the product as a white solid, containing diethyl ether (0.02 eq.) and hexane (0.02 eq.) (3.110 g).

(3H-Cyclopenta[a]naphthalen-3-yl)dimethyl(3-(pentan-2-yl)-1H-inden-1-yl)silane

To a stirring solution of dimethyl(3-(pentan-2-yl)-1H-inden-1-yl)silyl trifluoromethanesulfonate (0.680 g, 0.002 mol) in diethyl ether (20 mL), lithium 1H-cyclopenta[a]naphthalen-1-ide (0.308 g, 0.002 mol, 1.01 eq.) was added with diethyl ether (10 mL). The reaction was stirred at room temperature for 85 minutes. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (40 mL) and filtered over Celite. The pentane extract was concentrated under a stream of nitrogen and then under high vacuum to afford the product as an orange-yellow oil (0.693 g).

Lithium 3-(dimethyl(3-(pentan-2-yl)-1H-inden-1-id-1-yl)silyl)-3H-cyclopenta[a]naphthalen-3-ide

To a stirring solution of (3H-cyclopenta[a]naphthalen-3-yl)dimethyl(3-(pentan-2-yl)-1H-inden-1-yl)silane (0.693 g, 0.002 mol) in diethyl ether (20 mL), n-butyllithium (2.5 M in hexanes, 1.4 mL, 0.004 mol, 2.06 eq.) was added. The reaction was stirred at room temperature for 18 minutes. Volatiles were removed under a stream of nitrogen and then under high vacuum to afford the product as an orange-white solid, containing diethyl ether (0.68 eq.) (0.691 g).

Dimethylsilyl (3-(2-pentanyl)-indenyl) benz[e]indenyl zirconium(IV) Dichloride

To a stirring solution of lithium 3-(dimethyl(3-(pentan-2-yl)-1H-inden-1-id-1-yl)silyl)-3H-cyclopenta[a]naphthalen-3-ide (0.691 g, 0.001 mol) in diethyl ether (40 mL), zirconium(IV) chloride (0.341 g, 0.001 mol, 1 eq.) was added with diethyl ether (10 mL). The reaction was stirred at room temperature for 15 hours. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane (10 mL, then 5 mL) and filtered over Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum. The dichloromethane extract was washed with hexane (2×10 mL) and minimal dichloromethane to afford the product as an orange solid (0.077 g, 9%, 1:1:1.2:1.4 ratio of diastereomers A, B, C, and D). ¹H NMR (400 MHz, CD₂Cl₂): δ 8.09-8.04 (m, 4H), 7.80-6.91 (m, 40H), 6.27 (d, 1H, J=3.3 Hz), 6.22 (d, 1H, J=3.3 Hz), 6.21 (d, 1H, J=3.5 Hz), 6.16 (d, 1H, J=3.2 Hz), 6.02 (s, 1H, isomer A, used for isomer ratio), 6.00 (s, 1H, isomer C, used for isomer ratio), 5.95 (s, 1H, isomer B, used for isomer ratio), 5.90 (s, 1H, isomer D, used for isomer ratio), 3.25-3.15 (m, 1H), 3.15-3.06 (m, 1H), 3.06-2.97 (m, 1H), 2.96-2.86 (m, 1H), 1.78-1.58 (m, 4H), 1.55-0.75 (m, 60H).

Lithium 4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-ide

To a stirring solution of 4-phenyl-1,2,3,5-tetrahydro-s-indacene (1.916 g, 0.008 mol) in diethyl ether (20 mL), n-butyllithium (2.5 M in hexanes, 3.3 mL, 0.008 mol, 1 eq.) was added. The reaction was stirred at room temperature for 65 minutes. Volatiles were removed under a stream of nitrogen. The residue was washed with hexane (10 mL) and diethyl ether (4×2 mL) and then concentrated under high vacuum to afford the product as an off-white solid, containing diethyl ether (0.08 eq.) and hexane (0.03 eq.) (1.203 g).

Dimethyl(3-(pentan-2-yl)-1H-inden-1-yl)(4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl)silane

To a stirring solution of dimethyl(3-(pentan-2-yl)-1H-inden-1-yl)silyl trifluoromethanesulfonate (0.543 g, 0.001 mol) in diethyl ether (20 mL), lithium 4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-ide (0.348 g, 0.001 mol, 1.02 eq.) was added with diethyl ether (10 mL). The reaction was stirred at room temperature for 57 minutes. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane and filtered over Celite. The pentane extract was concentrated under a stream of nitrogen and then under high vacuum to afford the product as a pale orange oil (0.590 g).

Lithium 1-(dimethyl(3-(pentan-2-yl)-1H-inden-1-id-1-yl)silyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-ide

To a stirring solution of dimethyl(3-(pentan-2-yl)-1H-inden-1-yl)(4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl)silane (0.590 g, 0.001 mol) in diethyl ether (20 mL), n-butyllithium (2.5 M in hexanes, 1.0 mL, 0.003 mol, 2.01 eq.) was added. The reaction was stirred at room temperature for 28 minutes. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was washed with hexane (10 mL) and then concentrated under high vacuum to afford the product, containing diethyl ether (0.66 eq.), and hexane (1.13 eq.) (0.504 g).

Dimethylsilyl (3-(2-pentanyl)-indenyl) (4-phenyl-1,5,6,7-tetrahydro-s-indacenyl) zirconium(IV) Dichloride

To a stirring solution of lithium 1-(dimethyl(3-(pentan-2-yl)-1H-inden-1-id-1-yl)silyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-ide (0.504 g, 0.80 mmol) in diethyl ether (40 mL), zirconium(IV) chloride (0.221 g, 0.95 mmol, 1.19 eq.) was added. The reaction was stirred at room temperature for 16 hours. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane (10 mL, then 5 mL) and filtered over Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum. The extract was washed with hexane (2×10 mL). The washed dichloromethane extract was dissolved in minimal dichloromethane and diluted with pentane to facilitate precipitation. The supernatant was collected and concentrated under a stream of nitrogen and then under high vacuum to afford the product as an orange solid (0.199 g, 39%, 1:1:1.5:2.9 ratio of diastereomers A, B, C, and D). ¹H NMR (400 MHz, CD₂Cl₂): δ 7.61-6.60 (m, 44H), 6.06-6.03 (m, 3H), 5.96 (s, 1H), 5.94 (d, 1H, J=3.4 Hz), 5.93 (d, 1H, J=3.3 Hz), 5.83 (s, 1H), 5.73 (s, 1H), 3.24-2.71 (m, 20H), 2.06-1.85 (m, 8H), 1.83-1.59 (m, 4H), 1.51-0.77 (m, 60H). ¹H NMR (400 MHz, C₆D₆) (region 6-5.5 ppm used for determination of isomer ratio): 5.99 (s, 1H, isomer A, used for isomer ratio), 5.91 (s, 1H, isomer B, used for isomer ratio), 5.89 (d, 1H, J=3.4 Hz), 5.88 (d, 1H, J=3.2 Hz), 5.69 (s, 1H, isomer D, used for isomer ratio), 5.65 (d, 1H, J=3.3 Hz), 5.64 (s, 1H, isomer C, used for isomer ratio), 5.61 (d, 1H, J=3.3 Hz).

1-Isopropyl-1H-indene

To a precooled, stirring solution of lithium indenide (1.049 g, 0.009 mol) in tetrahydrofuran (20 mL), 2-bromopropane (4.2 mL, 0.045 mol, 5.2 eq.) was added. The reaction was stirred and heated to 58° C. for 2 hours. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane and filtered over Celite. The pentane extract was concentrated under a stream of nitrogen and then under high vacuum to afford the product as a yellow oil (1.001 g, as a 1:2 mixture of 1- and 3-alkylated indene regioisomers).

Lithium 1-isopropyl-1H-inden-1-ide

To a stirring solution of 1-isopropyl-1H-indene (0.454 g, 0.003 mol) in diethyl ether (15 mL), n-butyllithium (2.5 M in hexanes, 1.2 mL, 0.003 mol, 1.05 eq.) was added. The reaction was stirred at room temperature for 55 minutes. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was washed with hexane (10 mL) and concentrated under high vacuum to afford the product as a white solid, containing diethyl ether (0.04 eq.) and hexane (0.06 eq.) (0.477 g).

Chloro(3-isopropyl-1H-inden-1-yl)dimethylsilane

To a stirring solution of lithium 1-isopropyl-1H-inden-1-ide (0.477 g, 0.003 mol) in diethyl ether (20 mL), dichlorodimethylsilane (5.0 mL, 0.041 mol, 14.9 eq.) was added rapidly. The reaction was stirred at room temperature for 51 minutes. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (15 mL) and filtered over Celite. The extract was concentrated under a stream of nitrogen and then under high vacuum to afford the product as an orange oil (0.600 g).

(3-Isopropyl-1H-inden-1-yl)dimethylsilyl trifluoromethanesulfonate

To a stirring solution of chloro(3-isopropyl-1H-inden-1-yl)dimethylsilane (0.600 g, 0.002 mol) in toluene (10 mL), silver(I) trifluoromethanesulfonate (0.615 g, 0.002 mol, 1 eq.) was added. The reaction was stirred at room temperature for 25 minutes. The reaction was filtered over Celite. The filtrate was concentrated under high vacuum. The residue was extracted with pentane (10 mL) and filtered over Celite. The pentane extract was concentrated under a stream of nitrogen and then under high vacuum to afford the product as a colorless oil (0.755 g).

(3-Isopropyl-1H-inden-1-yl)dimethyl(3-methyl-1H-inden-1-yl)silane

To a stirring solution of lithium 1-methyl-1H-indenide (0.344 g, 0.003 mol, 1.22 eq.) in diethyl ether (20 mL), a solution of (3-isopropyl-1H-inden-1-yl)dimethylsilyl trifluoromethanesulfonate (0.755 g, 0.002 mol) in diethyl ether was added. The reaction was stirred at room temperature for 100 minutes. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (20 mL) and filtered over Celite. The filtrate was concentrated under a stream of nitrogen and then under high vacuum to afford the product as an oil (0.490 g).

Lithium 1-(dimethyl(3-methyl-1H-inden-1-id-1-yl)silyl)-3-isopropyl-1H-inden-1-ide

To a precooled, stirring solution of (3-isopropyl-1H-inden-1-yl)dimethyl(3-methyl-H-inden-1-yl)silane (0.490 g, 0.001 mol) in diethyl ether (30 mL), n-butyllithium (2.5 M in hexanes, 1.15 mL, 0.003 mol, 2.022 eq.) was added. The reaction was stirred at room temperature for 1h. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was washed with hexane (20 mL) and then concentrated under high vacuum to afford the product as a white solid, containing diethyl ether (1.28 eq.) (0.541 g).

Dimethylsilyl (3-isopropyl-indenyl) (3-methyl-indenyl) zirconium(IV) Dichloride

To a precooled, stirring suspension of lithium 1-(dimethyl(3-methyl-1H-inden-1-id-1-yl)silyl)-3-isopropyl-1H-inden-1-ide (0.541 g, 0.001 mol) in diethyl ether (30 mL), zirconium(IV) chloride 0.279 g, 0.001 mol, 1 eq.) was added. The reaction was stirred at room temperature for 15 hours. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane (15 mL) and filtered over Celite. The dichloromethane extract was concentrated under a stream of nitrogen and then under high vacuum to afford the product as an orange solid (0.506 g, 83%, 1:1.8 ratio of diastereomers A and B). ¹H NMR (400 MHz, CD₂Cl₂): δ 7.59-6.92 (m, 8H each diastereomer), 5.97 (s, 1H, A), 5.84 (s, 1H, A), 5.80 (s, 1H, B), 5.72 (s, 1H, B), 3.36 (hept, 1H, J=6.9 Hz, B), 3.17 (hept, 1H, J=6.8 Hz, A), 2.39 (s, 3H, isomer B, used for isomer ratio), 2.31 (s, 3H, isomer A, used for isomer ratio), 1.32 (s, 3H, B), 1.26 (d, 6H, J=6.9 Hz, B), 1.18 (d, 3H, J=7.0 Hz, A), 1.14 (s, 3H, A), 1.06 (s, 3H, A), 0.97 (d, 3H, J=6.7 Hz, A), 0.94 (s, 3H, B).

(1H-Inden-1-yl)(3-isopropyl-1H-inden-1-yl)dimethylsilane

To a stirring solution of (3-isopropyl-1H-inden-1-yl)dimethylsilyl trifluoromethanesulfonate (1.706 g, 0.005 mol) in diethyl ether (40 mL), lithium indenide (0.572 g, 0.005 mol, 1 eq.) was added. The reaction was stirred at room temperature for 15 hours. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (40 mL, then 10 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to afford the product as a yellow-orange oil (1.518 g).

Lithium 1-((1H-inden-1-id-1-yl)dimethylsilyl)-3-isopropyl-1H-inden-1-ide

To a stirring solution of (1H-inden-1-yl)(3-isopropyl-1H-inden-1-yl)dimethylsilane (1.518 g, 0.005 mol) in hexane (20 mL), n-butyllithium (2.5 M in hexanes, 3.8 mL, 0.009 mol, 2.07 eq.) was added. The reaction was stirred at room temperature for 49 minutes. The reaction was filtered, and the solid was collected and concentrated under high vacuum to afford the product as a white solid, containing diethyl ether (0.47 eq.) and hexane (0.45 eq.) (1.706 g).

Dimethylsilyl (3-isopropyl-indenyl) indenyl zirconium(IV) dichloride

To a stirring solution of lithium 1-((1H-inden-1-id-1-yl)dimethylsilyl)-3-isopropyl-1H-inden-1-ide (1.706 g, 0.004 mol) in diethyl ether (40 mL), zirconium(IV) chloride (0.954 g, 0.004 mol, 1 eq.) was added with diethyl ether (10 mL). The reaction was stirred for 103 minutes. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane (2×20 mL) and filtered over Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum. The residue was stirred in hexane. The mixture was then concentrated under a stream of nitrogen and then under high vacuum to afford the product as an orange powder (1.948 g, 96%, 1:1.2 ratio of diastereomers A and B). ¹H NMR (400 MHz, CD₂Cl₂): δ 7.64-6.92 (m, 17H), 6.79 (dd, 1H, J=3.2, 1.0 Hz), 6.17 (d, 1H, J=3.2 Hz, isomer A, used for isomer ratio), 6.13 (d, 1H, J=3.3 Hz, isomer B, used for isomer ratio), 5.96 (s, 1H), 5.90 (s, 1H), 3.29 (hept, 1H, J=7.1 Hz), 3.16 (hept, 1H, J=6.8 Hz), 1.32 (s, 3H), 1.29 (d, 3H, J=6.8 Hz), 1.26 (d, 3H, J=7.0 Hz), 1.16 (d, 3H, J=7.0 Hz), 1.16 (s, 3H), 1.09 (s, 3H), 0.98 (s, 3H), 0.94 (d, 3H, J=6.7 Hz).

1,2-Bis(3-butylcyclopenta-2,4-dien-1-yl)-1,1,2,2-tetramethyldisilane

To a precooled, stirring solution of lithium 1-butylcyclopentadienide (0.589 g, 4.60 mmol, 2 eq.) in tetrahydrofuran (10 mL), a precooled solution of 1,2-dichloro-1,1,2,2-tetramethyldisilane (0.430 g, 2.30 mmol) in tetrahydrofuran (5 mL) was added. The reaction was stirred at room temperature for 24 hours. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with hexane and filtered over Celite. The extract was concentrated under a stream of nitrogen and then under high vacuum to afford the product (0.542 g).

Lithium 1,1′-(1,1,2,2-tetramethyldisilane-1,2-diyl)bis(3-butylcyclopenta-2,4-dien-1-ide

To a precooled, stirring solution of 1,2-bis(3-butylcyclopenta-2,4-dien-1-yl)-1,1,2,2-tetramethyldisilane (0.542 g, 1.5 mmol) in diethyl ether (10 mL), n-butyllithium (2.5 M in hexanes, 1.24 mL, 3.1 mmol, 2.05 eq.) was added. The reaction was stirred at room temperature for 16h. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was washed with hexane (3×5 mL) and concentrated under high vacuum to afford the product as a solid (0.537 g).

Tetramethyldisilylene Bis(3-n-butylcyclopentadienyl) zirconium(IV) chloride

To a precooled, stirring suspension of zirconium(IV) chloride (0.343 g, 1.48 mmol, 1.02 eq.) in diethyl ether (10 mL), a precooled solution of lithium 1,1′-(1,1,2,2-tetramethyldisilane-1,2-diyl)bis(3-butylcyclopenta-2,4-dien-1-ide) (0.537 g, 1.45 mmol) in diethyl ether (20 mL) was added. The reaction was stirred at room temperature for 17 hours. Volatiles were removed under a stream of nitrogen and then under high vacuum. The residue was extracted with hexane. The hexane extract was concentrated under a stream of nitrogen and then high vacuum. The hexane extract was dissolved in hexane and cooled to −35° C. The precipitate was collected and washed with minimal cold hexane (5×1 mL). The cold hexane washed solid was concentrated under high vacuum to afford the product as a white solid (0.087 g, 11%, 1:4 ratio of diastereomers A and B). ¹H NMR (400 MHz, C₆D₆): δ 6.50 (t, 2H, J=2.1 Hz, isomer A, used for isomer ratio), 6.48 (dd, 2H, J=3.1, 2.3 Hz, isomer B, used for isomer ratio), 6.33 (t, 2H, J=2.2 Hz, B), 6.26 (dd, 2H, J=3.1, 2.0 Hz, B), 6.25-6.23 (m, 2H, A), 6.19 (dd, 2H, J=3.1, 2.3 Hz, A), 2.99-2.77 (m, 4H of A, 2H of B), 2.73-2.63 (m, 2H, B), 1.62-1.41 (m, 4H each of A and B), 1.33-1.21 (m, 4H each of A and B), 0.90-0.80 (m, 6H each of A and B), 0.28 (s, 6H, A), 0.28 (s, 6H, B), 0.27 (s, 6H, B), 0.24 (s, 6H, A).

Dimethylsilyl (3-(2-pentyl)-1,5,6,7-tetrahydro-s-indacenyl) (1,5,6,7-tetrahydro-s-indacenyl) Zirconium Dichloride

Dimethyl(3-(pentan-2-yl)-1,5,6,7-tetrahydro-s-indacen-1-yl)(1,5,6,7-tetrahydro-s-indacen-1-yl)silane

To a stirring solution of dimethyl(3-(pentan-2-yl)-1,5,6,7-tetrahydro-s-indacen-1-yl)silyl trifluoromethanesulfonate (1.629 g, 3.77 mmol) in diethyl ether (20 mL), lithium 1,5,6,7-tetrahydro-s-indacenide (0.617 g, 3.80 mmol, 1.01 eq) was added with diethyl ether (20 mL). The reaction was stirred at room temperature for 2h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (2×20 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to afford the product as a yellow-orange oil (1.592 g).

Lithium 1-((6,7-dihydro-s-indacen-1-id-1(5H)-yl)dimethylsilyl)-3-(pentan-2-yl)-1,5,6,7-tetrahydro-s-indacen-1-ide

To a stirring solution of dimethyl(3-(pentan-2-yl)-1,5,6,7-tetrahydro-s-indacen-1-yl)(1,5,6,7-tetrahydro-s-indacen-1-yl)silane (1.592 g, 3.63 mmol) in diethyl ether (20 mL), n-butyllithium (3.0 mL, 2.5M in hexanes, 7.49 mmol, 2.07 eq) was added. The reaction was stirred at room temperature for 55 minutes. The reaction was concentrated under a stream of nitrogen and then under high vacuum to afford the product as an amber-white foam, containing diethyl ether (0.85 eq) and hexane (0.51 eq) (2.024 g).

Dimethylsilyl (3-(2-pentyl)-1,5,6,7-tetrahydro-s-indacenyl) (1,5,6,7-tetrahydro-s-indacenyl) Zirconium Dichloride

To a stirring solution of lithium 1-((6,7-dihydro-s-indacen-1-id-1(5H)-yl)dimethylsilyl)-3-(pentan-2-yl)-1,5,6,7-tetrahydro-s-indacen-1-ide (0.882 g, 1.65 mmol) in diethyl ether (20 mL), zirconium(IV) chloride (0.376 g, 1.61 mmol, 0.98 eq) was added. The reaction was stirred at room temperature for 1h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane (10 mL, then 5 mL) and filtered over Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum to give a red foam. The foam was extracted with hexane (10 mL), and the hexane extract was concentrated under a stream of nitrogen and then under high vacuum to afford the product (0.472 g, 47%, ratio of 1.1:1.0:1.3:1.3 isomers A, B, C, and D, respectively). 1H NMR (400 MHz, CD2Cl2): δ 7.41-7.14 (m, 16H), 6.81 (dd, 1H, J=3.3, 0.9 Hz), 6.79 (dd, 1H, J=3.3, 0.9 Hz), 6.65 (dd, 1H, J=3.3, 0.9 Hz), 6.63 (dd, 1H, J=3.2, 0.8 Hz), 6.08-6.05 (m, 2H), 5.99 (d, 1H, J=3.3 Hz), 5.93 (d, 1H, J=3.2 Hz), 5.92 (s, 1H, isomer A, used for isomer ratio), 5.86 (s, 1H, isomer B, used for isomer ratio), 5.79 (s, 1H, isomer C, used for isomer ratio), 5.67 (s, 1H, isomer D, used for isomer ratio), 3.18-2.58 (m, 36H), 2.17-1.89 (m, 16H), 1.78-0.80 (m, 64H).

Dimethylsilyl (benz[e]inden-3-yl) (3-isopropyl-indenyl) Zirconium Dichloride

(3H-Cyclopenta[a]naphthalen-3-yl)(3-isopropyl-1H-inden-1-yl)dimethylsilane

To a stirring solution of (3-isopropyl-1H-inden-1-yl)dimethylsilyl trifluoromethanesulfonate (2.815 g, 7.72 mmol) in diethyl ether (20 mL), lithium benz[e]indenide (1.336 g, 7.76 mmol, 1.01 eq) was added with diethyl ether (20 mL). The reaction was stirred at room temperature for 31 minutes. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (3×20 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to afford the product as a pale orange oil, containing hexane (0.24 eq) (3.019 g).

Lithium 3-((3-isopropyl-1H-inden-1-id-1-yl)dimethylsilyl)-3H-cyclopenta[a]naphthalen-3-ide

To a stirring solution of (3H-cyclopenta[a]naphthalen-3-yl)(3-isopropyl-1H-inden-1-yl)dimethylsilane (3.019 g, 7.52 mmol) in diethyl ether (30 mL), n-butyllithium (6.4 mL, 2.5M in hexanes, 16.00 mmol, 2.13 eq) was added. The reaction was stirred at room temperature for 45 minutes. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was stirred in hexane (20 mL). The mixture was allowed to settle, and the hexane supernatant was decanted off. The hexane washed residue was concentrated under high vacuum to afford the product as a tan solid, containing diethyl ether (0.74 eq) and hexane (0.53 eq) (3.230 g).

Dimethylsilyl (benz[e]inden-3-yl) (3-isopropyl-indenyl) Zirconium Dichloride

To a stirring suspension of zirconium(IV) chloride (1.520 g, 6.52 mmol, 0.99 eq) in toluene (10 mL), lithium 3-((3-isopropyl-1H-inden-1-id-1-yl)dimethylsilyl)-3H-cyclopenta[a]naphthalen-3-ide (3.230 g, 6.56 mmol) was added with toluene (20 mL) and diethyl ether (1 mL). The reaction was stirred at room temperature for 18.5h. The reaction was filtered over a plastic frit and further washed with toluene (10 mL). The filtered solid was extracted with dichloromethane (20 mL, then 2×10 mL). The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum to afford the product as an orange solid (1.181 g, 33%, ratio of 2.1:1 isomers A and B). ¹H NMR (400 MHz, CD₂Cl₂): δ 8.10-8.03 (m, 2H), 7.78 (dd, 1H, J=7.8, 1.4 Hz), 7.72-7.67 (m, 1H), 7.64-7.25 (m, 15H), 7.17-7.08 (m, 2H), 6.97 (ddd, 1H, J=8.7, 6.7, 1.1 Hz), 6.21 (d, 1H, J=3.2 Hz, isomer A, used for isomer ratio), 6.18 (d, 1H, J=3.3 Hz, isomer B, used for isomer ratio), 6.00 (s, 2H), 3.29 (hept, 1H, J=6.9 Hz), 3.11 (hept, 1H, J=7.0 Hz), 1.34 (s, 3H), 1.32 (d, 3H, J=6.8 Hz), 1.25 (d, 3H, J=7.0 Hz), 1.18 (s, 3H), 1.16 (d, 3H, J=7.0 Hz), 1.12 (s, 3H), 1.00 (s, 3H), 0.95 (d, 3H, J=6.7 Hz).

Dimethylsilyl (benz[e]inden-3-yl) (3-(sec-butyl)-indenyl) Zirconium Dichloride

3-(sec-butyl)-1H-indene

To a stirring solution of lithium indenide (5.189 g, 42.50 mmol) in tetrahydrofuran (140 mL), 2-bromobutane (4.7 mL, 43.05 mmol, 1.01 eq) was added. The reaction was stirred and heated to 60° C. for 15h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane and filtered over Celite. The pentane extract was concentrated under a stream of nitrogen and then under high vacuum to give a yellow oil. The oil was purified by silica gel column chromatography, eluting with isohexane, to afford the product as a clear, colorless oil (4.401 g).

Lithium 1-(sec-butyl)-1H-inden-1-ide

To a stirring solution of 3-(sec-butyl)-1H-indene (4.401 g, 25.55 mmol) in diethyl ether (40 mL), n-butyllithium (10.4 mL, 2.5M in hexanes, 25.99 mmol, 1.02 eq) was added. The reaction was stirred at room temperature for 2h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was washed with pentane (2×20 mL) and concentrated under high vacuum to afford the product as a pale yellow solid, containing diethyl ether (0.04 eq) and hexane (0.15 eq) (4.203 g).

(3-(Sec-butyl)-1H-inden-1-yl)chlorodimethylsilane

To a stirring solution of dichlorodimethylsilane (10.0 mL, 82.91 mmol, 14.50 eq) in diethyl ether (40 mL), lithium 1-(sec-butyl)-1H-inden-1-ide (1.019 g, 5.72 mmol) was added. The reaction was stirred at room temperature for 16.5h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (2×20 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to afford the product as a clear, colorless oil (1.446 g).

(3-(Sec-butyl)-1H-inden-1-yl)dimethylsilyl Trifluoromethanesulfonate

To a stirring solution of (3-(sec-butyl)-1H-inden-1-yl)chlorodimethylsilane (1.446 g, 5.46 mmol) in toluene (10 mL), silver(I) trifluoromethanesulfonate (1.405 g, 5.47 mmol, 1 eq) was added with toluene (10 mL). The reaction was stirred at room temperature for 20 minutes. The reaction was filtered over Celite. The filtrate was concentrated over high vacuum at 40° C. to afford the product as a brown oil (1.944 g).

(3-(Sec-butyl)-1H-inden-1-yl)(3H-cyclopenta[a]naphthalen-3-yl)dimethylsilane

To a stirring solution of (3-(sec-butyl)-1H-inden-1-yl)dimethylsilyl trifluoromethanesulfonate (1.944 g, 5.14 mmol) in diethyl ether (20 mL), lithium benz[e]indenide (0.883 g, 5.13 mmol, 1 eq) was added with diethyl ether (20 mL). The reaction was stirred at room temperature for 70 minutes. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (2×20 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to afford the product as a white oil (1.999 g).

Lithium 3-((3-(sec-butyl)-1H-inden-1-id-1-yl)dimethylsilyl)-3H-cyclopenta[a]naphthalen-3-ide

To a stirring solution of (3-(sec-butyl)-1H-inden-1-yl)(3H-cyclopenta[a]naphthalen-3-yl)dimethylsilane (1.999 g, 5.07 mmol) in diethyl ether (20 mL), n-butyllithium (4.1 mL, 2.5M in hexanes, 10.26 mmol, 2.02 eq) was added. The reaction was stirred at room temperature for 19 minutes. The reaction was concentrated under a stream of nitrogen and then under high vacuum to afford the product as an orange foam, containing diethyl ether (0.94 eq) and hexane (0.33 eq) (2.629 g).

Dimethylsilyl (benz[e]inden-3-yl) (3-(sec-butyl)-indenyl) Zirconium Dichloride

To a stirring suspension of zirconium(IV) chloride (1.213 g, 5.205 mmol, 1 eq) in diethyl ether (20 mL), a solution of lithium 3-((3-(sec-butyl)-1H-inden-1-id-1-yl)dimethylsilyl)-3H-cyclopenta[a]naphthalen-3-ide (2.629 g, 5.213 mmol) in diethyl ether (20 mL) was added. The reaction was stirred at room temperature for 15h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane and filtered over Celite. The dichloromethane extract was concentrated under a stream of nitrogen and then under high vacuum. The residue was washed with hexane and concentrated under high vacuum to give an orange solid. Dichloromethane (3 mL) was added to the orange solid, and the mixture was stirred. The mixture was diluted with hexane (20 mL). The resulting suspension was allowed to settle. The supernatant was removed, and the remaining solid was concentrated under high vacuum to afford the product as a yellow-orange solid (1.828 g, 63%, ratio of 1.0:1.4:1.6:2.2 isomers A, B, C, and D). ¹H NMR (400 MHz, C₆D₆): δ 8.02-7.97 (m, 1H), 7.96-7.85 (m, 3H), 7.58-6.70 (m, 40H), 6.02 (d, 2H, J=3.2 Hz), 5.93 (s, 1H, isomer D, used for isomer ratio), 5.85 (s, 1H, isomer C, used for isomer ratio), 5.82 (s, 1H, isomer A, used for isomer ratio), 5.80 (d, 1H, J=3.2 Hz), 5.75 (d, 1H, J=3.2 Hz), 5.73 (s, 1H, isomer B, used for isomer ratio), 3.37-3.09 (m, 3H), 3.04-2.92 (m, 1H), 1.93-1.80 (m, 1H), 1.76-1.64 (m, 1H), 1.61-1.25 (m, 15H), 1.00 (d, 3H, J=6.7 Hz), 0.92 (t, 3H, J=7.3 Hz), 0.82-0.74 (m, 12H), 0.68-0.60 (m, 15H), 0.49 (s, 3H), 0.44 (s, 3H).

Dimethylsilyl (benz[e]inden-3-yl) (3-(sec-butyl)-indenyl) Hafnium Dimethyl

Dimethylsilyl (benz[e]inden-3-yl) (3-(sec-butyl)-indenyl) hafnium dichloride

To a stirring suspension of hafnium(IV) chloride (1.117 g, 3.49 mmol, 1.01 eq) in diethyl ether (40 mL), a solution of lithium 3-((3-(sec-butyl)-1H-inden-1-id-1-yl)dimethylsilyl)-3H-cyclopenta[a]naphthalen-3-ide (1.616 g, 3.47 mmol) in diethyl ether (20 mL) was added. The reaction was stirred at room temperature for 2h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane (2×20 mL) and filtered over Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum to give a bright yellow solid. The solid was stirred in hexane (10 mL) to form a bright yellow suspension. The suspension was filtered on a plastic frit. The filtered solid was washed with additional hexane (2×10 mL). The filtered solid was collected and concentrated under high vacuum to afford the product as a bright yellow solid (1.463 g, 65%, ratio of 1.0:1.3:1.7:2.3 isomers A, B, C, and D). ¹H NMR (400 MHz, CD₂Cl₂): δ 8.07-8.00 (m, 4H), 7.81-6.87 (m, 40H), 6.23 (d, 1H, J=3.3 Hz), 6.19 (d, 1H, J=3.2 Hz), 6.16 (d, 1H, J=3.3 Hz), 6.14 (d, 1H, J=3.1 Hz), 6.05 (s, 1H, isomer A, used for isomer ratio), 5.99 (s, 1H, isomer D, used for isomer ratio), 5.93 (s, 1H, isomer B, used for isomer ratio), 5.88 (s, 1H, isomer C, used for isomer ratio), 3.23-3.13 (m, 1H), 3.08-2.92 (m, 2H), 2.82 (h, 1H, J=6.9 Hz), 1.85-1.27 (m, 17H), 1.22 (d, 3H, J=7.0 Hz), 1.18 (s, 3H), 1.13 (s, 3H), 1.13 (s, 3H), 1.10 (s, 3H), 1.02 (s, 3H), 0.99-0.93 (m, 6H), 0.86 (s, 3H), 0.85 (s, 3H), 0.81 (t, 3H, J=7.4 Hz), 0.78 (t, 3H, J=7.4 Hz), 0.72 (t, 3H, J=7.4 Hz).

Dimethylsilyl (benz[e]inden-3-yl) (3-(sec-butyl)-indenyl) Hafnium Dimethyl

To a stirring suspension of dimethylsilyl (benz[e]inden-3-yl) (3-(sec-butyl)-indenyl) hafnium dichloride (1.463 g) in diethyl ether (80 mL), methylmagnesium bromide (3.8 mL, 3.0M in diethyl ether, 11.40 mmol, 5 eq) was added. The reaction was stirred at room temperature for 15.5h. The reaction was found to be incomplete; therefore, the reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was stirred in toluene with additional methylmagnesium bromide (3.8 mL, 5 eq) and heated to 75° C. for 3 days. The reaction was allowed to cool to room temperature, and then the reaction was concentrated under high vacuum at 30° C. The residue was extracted with hot hexane (50 mL, then 20 mL) and filtered over Celite. The combined hot hexane extracts were concentrated under a stream of nitrogen and then under high vacuum to afford the product as a pale yellow foam (1.000 g, 72%, ratio of 1.0:1.3:1.5:2.3 isomers A, B, C, and D). ¹H NMR (400 MHz, C₆D₆): δ 8.12-8.05 (m, 2H), 7.96-7.90 (m, 2H), 7.61-6.79 (m, 40H), 5.84-5.79 (m, 3H), 5.72 (s, 1H), 5.70 (s, 1H), 5.66 (s, 1H), 5.64 (s, 1H), 5.58 (d, 1H, J=3.2 Hz), 3.24-3.11 (m, 1H), 2.97-2.87 (m, 2H), 2.76-2.66 (m, 1H), 1.87-0.51 (m, 56H), −0.22 (s, 3H, isomer A, used for isomer ratio), −0.25 (s, 3H, isomer B, used for isomer ratio), −1.18 (s, 3H, isomer C, used for isomer ratio), −1.23 (s, 3H, isomer D, used for isomer ratio), −1.39 (s, 3H), −1.43 (s, 3H), −2.59 (s, 3H), −2.60 (s, 3H).

Dimethylsilyl (benz[e]inden-3-yl) (3-isopropyl-1,5,6,7-tetrahydro-s-indacenyl) Zirconium Dichloride

7-Isopropyl-1,2,3,5-tetrahydro-s-indacene

To a stirring solution of lithium 1,5,6,7-tetrahydro-s-indacenide (0.644 g, 3.97 mmol) in tetrahydrofuran (20 mL), 2-bromopropane (0.38 mL, 4.05 mmol, 1.02 eq) was added. The reaction was stirred and heated to 55° C. overnight. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane and filtered over Celite. The pentane extract was concentrated under a stream of nitrogen and then under high vacuum to afford the product (0.733 g).

Lithium 1-isopropyl-1,5,6,7-tetrahydro-s-indacen-1-ide

To a stirring solution of 7-isopropyl-1,2,3,5-tetrahydro-s-indacene (0.733 g, 3.70 mmol) in diethyl ether (20 mL), n-butyllithium (1.5 mL, 2.5M in hexanes, 3.75 mmol, 1.02 eq) was added. The reaction was stirred at room temperature for 2h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was washed with hexane and concentrated under high vacuum to afford the product as a white solid (0.750 g).

Chloro(3-isopropyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethylsilane

To a stirring solution of lithium 1-isopropyl-1,5,6,7-tetrahydro-s-indacen-1-ide (0.750 g, 3.67 mmol) in diethyl ether (20 mL), dichlorodimethylsilane (6.6 mL, 54.72 mmol, 14.90 eq) was added rapidly. The reaction was stirred at room temperature for 100 minutes. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (3×10 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to afford the product (0.948 g).

(3-Isopropyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethylsilyl Trifluoromethanesulfonate

To a stirring solution of chloro(3-isopropyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethylsilane (0.948 g, 3.26 mmol) in toluene (10 mL), silver(I) trifluoromethanesulfonate (0.834 g, 3.25 mmol, 1 eq) was added with toluene (10 mL). The reaction was stirred at room temperature for 22 minutes. The reaction was filtered over Celite. The solid was extracted further with toluene (10 mL). The combined toluene extracts were concentrated under high vacuum at 45° C. to afford the product as a dark oil (1.247 g).

(3H-Cyclopenta[a]naphthalen-3-yl)(3-isopropyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethylsilane

To a stirring solution of (3-isopropyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethylsilyl trifluoromethanesulfonate (1.247 g, 3.08 mmol) in diethyl ether (20 mL), lithium benz[e]indenide (0.534 g, 3.10 mmol, 1.01 eq) was added with diethyl ether (10 mL). The reaction was stirred at room temperature for 20 minutes. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (20 mL, then 2×10 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to afford the product as a white foam (1.301 g).

Lithium 3-((3-isopropyl-6,7-dihydro-s-indacen-1-id-1(5H)-yl)dimethylsilyl)-2,3-dihydro-1H-cyclopenta[a]naphthalen-3-ide

To a stirring solution of (3H-cyclopenta[a]naphthalen-3-yl)(3-isopropyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethylsilane (1.301 g, 3.09 mmol) in diethyl ether (20 mL), n-butyllithium (2.5 mL, 2.5M in hexanes, 6.24 mmol, 2.02 eq) was added. The reaction was stirred at room temperature for 17 minutes. The reaction was concentrated under a stream of nitrogen and then under high vacuum to afford the product as an orange foam, containing diethyl ether (1.09 eq) and hexane (0.52 eq) (1.768 g).

Dimethylsilyl (benz[e]inden-3-yl) (3-isopropyl-1,5,6,7-tetrahydro-s-indacenyl) Zirconium Dichloride

To a stirring solution of lithium 3-((3-isopropyl-6,7-dihydro-s-indacen-1-id-1(5H)-yl)dimethylsilyl)-2,3-dihydro-1H-cyclopenta[a]naphthalen-3-ide (1.768 g, 3.17 mmol) in toluene (10 mL), zirconium (IV) chloride (0.724 g, 3.11 mmol, 0.98 eq) was added with toluene (10 mL). The reaction was stirred at room temperature for 15h. The reaction was filtered over Celite. The solid was further washed with toluene (10 mL). The filtered solid was extracted with dichloromethane (2×20 mL, then 3×10 mL). The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum to afford the product as an orange solid (1.298 g, 70%, ratio of 1:1.1 isomers A and B). ¹H NMR (400 MHz, CD₂Cl₂): δ 8.10-8.01 (m, 2H), 7.76 (m, 1H), 7.71-7.67 (m, 1H), 7.60 (td, 1H, J=7.6, 1.5 Hz), 7.53 (m, 2H), 7.50-7.41 (m, 3H), 7.41-7.20 (m, 8H), 6.21-6.15 (m, 2H), 5.91 (s, 1H), 5.90 (s, 1H), 3.24 (hept, 1H, J=6.8 Hz), 3.12-2.63 (m, 9H), 2.14-1.88 (m, 4H), 1.31 (s, 3H), 1.29 (d, 3H, J=6.7 Hz), 1.22 (d, 3H, J=6.9 Hz), 1.16 (s, 3H), 1.13 (d, 3H, J=6.9 Hz), 1.10 (s, 3H), 0.98 (s, 3H), 0.90 (d, 3H, J=6.6 Hz). ¹H NMR (400 MHz, C₆D₆) (region 6.1-5.7 ppm used for determination of isomer ratio): δ 6.06 (d, 1H, J=3.2 Hz), 5.92 (s, 1H, isomer B, used for isomer ratio), 5.80 (s, 1H, isomer A, used for isomer ratio), 5.76 (d, 1H, J=3.3 Hz).

Dimethylsilyl (benz[e]inden-3-yl) (3-(sec-butyl)-1,5,6,7-tetrahydro-s-indacenyl) Zirconium Dichloride

7-(Sec-butyl)-1,2,3,5-tetrahydro-s-indacene

To a stirring solution of lithium 1,5,6,7-tetrahydro-s-indacenide (2.134 g, 13.03 mmol) in tetrahydrofuran (40 mL), 2-bromobutane (1.45 mL, 13.28 mmol, 1.02 eq) was added. The reaction was stirred and heated to 60° C. for 21.5h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with hexane (40 mL, then 20 mL) and filtered over Celite. The combined hexane extracts were concentrated under a stream of nitrogen and then under high vacuum to give a yellow oil. The oil was purified by silica gel column chromatography, eluting with isohexane, to afford the product as a clear, colorless oil (2.527 g).

Lithium 1-(sec-butyl)-1,5,6,7-tetrahydro-s-indacenide

To a stirring solution of 1-(sec-butyl)-1,5,6,7-tetrahydro-s-indacene (1.573 g, 7.41 mmol) in diethyl ether, n-butyllithium (3.0 mL, 2.5M in hexanes, 7.50 mmol, 1.01 eq) was added. The reaction was stirred at room temperature for 16.5h. The reaction was filtered over a plastic fritted funnel. The solid was washed with diethyl ether (5 mL). The solid was collected and concentrated under high vacuum to afford the product as a white solid (1.229 g).

(3-(Sec-butyl)-1,5,6,7-tetrahydro-s-indacen-1-yl)chlorodimethylsilane

To a stirring suspension of lithium 1-(sec-butyl)-1,5,6,7-tetrahydro-s-indacenide (1.229 g, 5.63 mmol) in diethyl ether (20 mL), a solution of dichlorodimethylsilane (10.2 mL, 84.57 mmol, 15.02 eq) in diethyl ether (20 mL) was added. The reaction was stirred at room temperature for 18.5h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (20 mL, then 10 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to afford the product as a yellow oil (1.642 g).

(3-(Sec-butyl)-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethylsilyl Trifluoromethanesulfonate

To a stirring solution of (3-(sec-butyl)-1,5,6,7-tetrahydro-s-indacen-1-yl)chlorodimethylsilane (1.642 g, 5.39 mmol) in toluene (10 mL), silver(I) trifluoromethanesulfonate (1.384 g, 5.39 mmol, 1 eq) was added with toluene (10 mL). The reaction was stirred at room temperature for 1h. The reaction was filtered over Celite. The filtered solid was further extracted with toluene (2×5 mL). The combined toluene extracts were concentrated under high vacuum at 35° C. to afford the product as a clear, colorless oil (2.118 g).

(3-(Sec-butyl)-1,5,6,7-tetrahydro-s-indacen-1-yl)(3H-cyclopenta[a]naphthalen-3-yl)dimethylsilane

To a stirring solution of (3-(sec-butyl)-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethylsilyl trifluoromethanesulfonate (0.975 g, 2.33 mmol) in diethyl ether (10 mL), lithium benz[e]indenide (0.401 g, 2.33 mmol, 1 eq) was added with diethyl ether (10 mL). The reaction was stirred at room temperature for 14.5h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (20 mL, then 10 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to afford the product as a white foam (1.003 g).

Dimethylsilyl (benz[e]inden-3-yl) (3-(sec-butyl)-1,5,6,7-tetrahydro-s-indacenyl) Zirconium Dichloride

To a stirring solution of (3-(sec-butyl)-1,5,6,7-tetrahydro-s-indacen-1-yl)(3H-cyclopenta[a]naphthalen-3-yl)dimethylsilane (1.003 g, 2.31 mmol) in hexane (20 mL), n-butyllithium (1.9 mL, 2.5M in hexanes, 4.75 mmol, 2.06 eq) was added. The reaction was stirred at room temperature for 20h. The reaction was filtered over a plastic frit. The filtered solid was collected and concentrated under a high vacuum to afford the dilithiate as a white powder. The powder was dissolved in diethyl ether (20 mL) and stirred. To this solution, zirconium(IV) chloride (0.537 g, 2.31 mmol, 1 eq) was added with diethyl ether (20 mL). The reaction was stirred at room temperature for 18h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane (20 mL) and filtered over Celite. The dichloromethane extract was concentrated under a stream of nitrogen and then under high vacuum to give a red-orange solid. The solid was triturated in pentane (5 mL). The solid was collected and concentrated under high vacuum to afford the product as an orange solid (0.878 g, 64%, ratio of 1.0:1.2:1.3:1.4 isomers A, B, C, and D). ¹H NMR (400 MHz, CD₂Cl₂): δ 8.09-8.02 (m, 4H), 7.81-7.18 (m, 32H), 6.22 (d, 1H, J=3.3 Hz), 6.19 (d, 2H, J=3.3 Hz), 6.14 (d, 1H, J=3.2 Hz), 5.94 (s, 1H, isomer D, used for isomer ratio), 5.91 (s, 1H, isomer C, used for isomer ratio), 5.83 (s, 1H, isomer B, used for isomer ratio), 5.82 (s, 1H, isomer A, used for isomer ratio), 3.15-2.67 (m, 20H), 2.13-1.65 (m, 12H), 1.53-0.70 (m, 52H).

Dimethylsilyl (benz[e]inden-3-yl) (3-(2-pentyl)-1,5,6,7-tetrahydro-s-indacenyl) Zirconium Dichloride

Lithium 3-(dimethyl(3-(pentan-2-yl)-6,7-dihydro-s-indacen-1-id-1(5H)-yl)silyl)-3H-cyclopenta[a]naphthalen-3-ide

To a stirring solution of dimethyl(3-(pentan-2-yl)-1,5,6,7-tetrahydro-s-indacen-1-yl)silyl trifluoromethanesulfonate (0.339 g, 0.784 mmol) in diethyl ether (20 mL), lithium benz[e]indenide (0.139 g, 0.807 mmol, 1.03 eq) was added with diethyl ether (20 mL). The reaction was stirred at room temperature for 13.5h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (20 mL) and filtered over Celite. The pentane extract was concentrated under a stream of nitrogen and then under high vacuum to afford a clear, colorless oil. The oil was dissolved in diethyl ether (20 mL) and cooled to −35° C. To the cooled, stirring solution, n-butyllithium (0.63 mL, 2.5M in hexanes, 1.58 mmol, 2.01 eq) was added. The reaction was stirred at room temperature for 80 minutes. The reaction was concentrated under a stream of nitrogen and then under high vacuum to afford the product as a light orange foam, containing diethyl ether (0.69 eq) and hexane (0.91 eq) (0.423 g).

Dimethylsilyl (benz[e]inden-3-yl) (3-(2-pentyl)-1,5,6,7-tetrahydro-s-indacenyl) Zirconium Dichloride

To a stirring solution of lithium 3-(dimethyl(3-(pentan-2-yl)-6,7-dihydro-s-indacen-1-id-1(5H)-yl)silyl)-3H-cyclopenta[a]naphthalen-3-ide (0.423 g, 0.716 mmol) in diethyl ether (20 mL), zirconium(IV) chloride (0.167 g, 0.716 mmol, 1 eq) was added. The reaction was stirred at room temperature for 105 minutes. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane (10 mL, then 5 mL) and filtered over Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum to give a red-orange foam. The foam was washed with hexane (2 mL) and concentrated under high vacuum to afford the product as an orange solid (0.048 g, 11%, ratio of 1.0:1.1:1.2:1.4 isomers A, B, C, and D). ¹H NMR (400 MHz, CD₂Cl₂): δ 8.10-8.03 (m, 4H), 7.80-7.19 (m, 32H), 6.24 (d, 1H, J=3.2 Hz), 6.20-6.17 (m, 2H), 6.14 (d, 1H, J=3.2 Hz), 5.94 (s, 1H, isomer C, used for isomer ratio), 5.91 (s, 1H, isomer D, used for isomer ratio), 5.86 (s, 1H, isomer B, used for isomer ratio), 5.83 (s, 1H, isomer A, used for isomer ratio), 3.20-2.65 (m, 20H), 2.14-1.89 (m, 8H), 1.77-0.74 (m, 64H).

Dimethylsilyl (indenyl) (3-isopropyl-1,5,6,7-tetrahydro-s-indacenyl) Zirconium Dichloride

(1H-Inden-1-yl)(3-isopropyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethylsilane

To a stirring solution of (3-isopropyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethylsilyl trifluoromethanesulfonate (0.559 g, 1.38 mmol) in diethyl ether (5 mL), lithium indenide (0.169 g, 1.38 mmol, 1 eq) was added with diethyl ether (5 mL). The reaction was stirred at room temperature for 2h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (2×10 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to afford the product as a yellow oil, containing diethyl ether (0.01 eq) and pentane (0.17 eq) (0.476 g).

Lithium 1-((1H-inden-1-id-1-yl)dimethylsilyl)-3-isopropyl-1,5,6,7-tetrahydro-s-indacen-1-ide

To a stirring solution of (1H-inden-1-yl)(3-isopropyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethylsilane (0.476 g, 1.24 mmol) in diethyl ether (20 mL), n-butyllithium (1.0 mL, 2.5M in hexanes, 2.50 mmol, 2.01 eq) was added. The reaction was stirred at room temperature for 80 minutes. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was washed with hexane (10 mL) and concentrated under high vacuum to afford the product as a tan solid, containing diethyl ether (0.57 eq) and hexane (0.34 eq) (0.574 g).

Dimethylsilyl (indenyl) (3-isopropyl-1,5,6,7-tetrahydro-s-indacenyl) Zirconium Dichloride

To a stirring solution of lithium 1-((1H-inden-1-id-1-yl)dimethylsilyl)-3-isopropyl-1,5,6,7-tetrahydro-s-indacen-1-ide (0.574 g, 1.27 mmol) in diethyl ether (20 mL), zirconium(IV) chloride (0.290 g, 1.25 mmol, 0.98 eq) was added. The reaction was stirred at room temperature for 6h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane (10 mL, then 5 mL) and filtered over Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum to give a red oil. Hexane was added to the oil, and the mixture was stirred until the mixture had completely formed an orange suspension. The suspension was allowed to settle, and the hexane extract was separated from the precipitate. The hexane washed solid was concentrated under high vacuum to afford the product as an orange solid (0.496 g, 73%, ratio of 1.0:1.2 isomers A and B). ¹H NMR (400 MHz, C₆D₆): δ 7.47 (dt, 1H, J=8.6, 1.0 Hz), 7.41 (dt, 1H, J=8.6, 1.0 Hz), 7.38-7.31 (m, 4H), 7.22 (d, 1H, J=1.3 Hz), 7.19 (d, 1H, J=1.3 Hz), 7.06 (ddd, 1H, J=8.6, 6.7, 1.0 Hz), 6.98 (ddd, 1H, J=8.6, 6.7, 1.0 Hz), 6.94 (dd, 1H, J=3.3, 0.9 Hz), 6.81-6.76 (m, 2H), 6.75 (dd, 1H, J=3.3, 1.0 Hz), 6.00 (d, 1H, J=3.2 Hz), 5.86 (s, 1H), 5.72-5.67 (m, 2H), 3.51 (hept, 1H, J=6.8 Hz, isomer A, used for isomer ratio), 3.40 (hept, 1H, J=6.9 Hz, isomer B, used for isomer ratio), 2.97-2.54 (m, 8H), 2.00-1.88 (m, 1H), 1.85-1.63 (m, 3H), 1.41 (d, 3H, J=6.7 Hz), 1.29 (d, 3H, J=7.0 Hz), 1.16 (d, 3H, J=7.0 Hz), 1.06 (d, 3H, J=6.7 Hz), 0.86 (s, 3H), 0.67 (s, 3H), 0.63 (s, 3H), 0.49 (s, 3H).

Dimethylsilyl (indenyl) (3-sec-butyl-1,5,6,7-tetrahydro-s-indacenyl) Zirconium Dichloride

(3-(Sec-butyl)-1,5,6,7-tetrahydro-s-indacen-1-yl)(1H-inden-1-yl)dimethylsilane

To a stirring solution of (3-(sec-butyl)-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethylsilyl trifluoromethanesulfonate (4.801 g, 11.26 mmol) in diethyl ether (60 mL), lithium indenide (1.395 g, 11.43 mmol, 1.02 eq) was added with diethyl ether (20 mL). The reaction was stirred at room temperature for 14h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with hexane (3×20 mL) and filtered over Celite. The combined hexane extracts were concentrated under a stream of nitrogen and then under high vacuum to give an oil. The oil was purified by silica gel column chromatography to afford the product as a pale yellow oil (2.408 g).

Dimethylsilyl (indenyl) (3-sec-butyl-1,5,6,7-tetrahydro-s-indacenyl) Zirconium Dichloride

To a stirring solution of (3-(sec-butyl)-1,5,6,7-tetrahydro-s-indacen-1-yl)(1H-inden-1-yl)dimethylsilane (2.408 g, 6.26 mmol) in diethyl ether (30 mL), n-butyllithium (5.1 mL, 2.5M in hexanes, 12.75 mmol, 2.04 eq) was added. The reaction was stirred at room temperature for 10 minutes. The reaction was concentrated under a stream of nitrogen and then under high vacuum to give an orange-white foam. The foam was dissolved in toluene (20 mL) and added to a stirring suspension of zirconium(IV) chloride (1.455 g, 6.24 mmol, 1 eq) in toluene (20 mL). The reaction was stirred at room temperature for 14h. The reaction was filtered over Celite. The filtered solid was further extracted with toluene (2×10 mL). The combined toluene extracts were concentrated under high vacuum at 30° C. to give a light brown solid. The solid was washed with hexane (20 mL, then 2×10 mL) and filtered on a plastic fritted funnel. The solid was collected and concentrated under high vacuum to afford the product as an orange solid (2.474 g, 72%, ratio of 1.0:1.1:1.1:1.1 isomers A, B, C, and D). ¹H NMR (400 MHz, C₆D₆): δ 7.50-7.32 (m, 12H), 7.25-7.19 (m, 4H), 7.10-7.04 (m, 2H), 7.01-6.93 (m, 4H), 6.86-6.70 (m, 6H), 6.02-5.99 (m, 2H), 5.89 (s, 1H, isomer A, used for isomer ratio), 5.81 (s, 1H, isomer B, used for isomer ratio), 5.76 (d, 1H, J=3.3 Hz), 5.73 (s, 1H, isomer C, used for isomer ratio), 5.72 (d, 1H, J=3.4 Hz), 5.66 (s, 1H, isomer D, used for isomer ratio), 3.45-3.05 (m, 4H), 2.98-2.55 (m, 16H), 2.02-1.20 (m, 25H), 1.05 (d, 3H, J=6.7 Hz), 1.00 (t, 3H, J=7.4 Hz), 0.94 (t, 3H, J=7.3 Hz), 0.86 (s, 6H), 0.83 (t, 3H, J=7.4 Hz), 0.72 (t, 3H, J=7.5 Hz), 0.67 (s, 3H), 0.66 (s, 3H), 0.65 (s, 3H), 0.63 (s, 3H), 0.50 (s, 3H), 0.46 (s, 3H).

Dimethylsilyl (3-isopropyl-indenyl) (1,5,6,7-tetrahydro-s-indacenyl) Zirconium Dichloride

(3-Isopropyl-1H-inden-1-yl)dimethyl(1,5,6,7-tetrahydro-s-indacen-1-yl)silane

To a stirring solution of (3-isopropyl-1H-inden-1-yl)dimethylsilyl trifluoromethanesulfonate (0.263 g, 0.72 mmol) in diethyl ether (10 mL), lithium 1,5,6,7-tetrahydro-s-indacenide (0.141 g, 0.71 mmol, 0.98 eq) was added with diethyl ether (10 mL). The reaction was stirred at room temperature for 30 minutes. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (2×10 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to afford the product as a pale yellow oil, containing diethyl ether (0.04 eq) and pentane (0.15 eq) (0.261 g).

Dimethylsilyl (3-isopropyl-indenyl) (1,5,6,7-tetrahydro-s-indacenyl) Zirconium Dichloride

To a stirring solution of (3-isopropyl-1H-inden-1-yl)dimethyl(1,5,6,7-tetrahydro-s-indacen-1-yl)silane (0.261 g, 0.68 mmol) in diethyl ether (20 mL), n-butyllithium (0.55 mL, 2.5M in hexanes, 1.38 mmol, 2.03 eq) was added. The reaction was stirred at room temperature for 25 minutes. Then, more n-butyllithium (0.25 mL, 2.5M in hexanes, 0.63 mmol, 0.92 eq) was added. The reaction was stirred at room temperature for an additional 14.5h. The reaction was concentrated under a stream of nitrogen and then under high vacuum to give a tan solid. The solid was dissolved in diethyl ether (20 mL) and cooled to −35° C. This solution was added to a precooled, stirring suspension of zirconium(IV) chloride (0.177 g, 0.76 mmol, 1.12 eq) in diethyl ether (10 mL). The reaction was stirred at room temperature for 3.5h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane (10 mL, then 5 mL) and filtered over Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum to give a red-orange solid. The solid was washed with pentane (10 mL) and concentrated under high vacuum to afford the product as an orange powder (0.248 g, 68%, ratio of 1.0:1.3 isomers A and B). ¹H NMR (400 MHz, C₆D₆): δ 7.49 (dt, 1H, J=8.7, 1.0 Hz), 7.44 (dt, 1H, J=8.7, 1.0 Hz), 7.34-7.28 (m, 2H), 7.28 (br s, 2H), 7.24 (br s, 1H), 7.23 (br s, 1H), 7.19-7.13 (m, 1H), 7.02-6.94 (m, 2H), 6.92 (dd, 1H, J=3.3, 0.9 Hz), 6.77 (ddd, 1H, J=8.7, 6.7, 1.0 Hz), 6.72 (dd, 1H, J=3.3, 0.7 Hz), 5.98 (d, 1H, J=3.3 Hz), 5.93 (s, 1H, isomer B, used for isomer ratio), 5.73 (s, 1H, isomer A, used for isomer ratio), 5.67 (d, 1H, J=3.3 Hz), 3.49 (hept, 1H, J=6.8 Hz), 3.36 (hept, 1H, J=6.9 Hz), 2.91-2.50 (m, 8H), 1.89-1.60 (m, 4H), 1.38 (d, 3H, J=6.7 Hz), 1.26 (d, 3H, J=7.0 Hz), 1.15 (d, 3H, J=7.0 Hz), 1.04 (d, 3H, J=6.7 Hz), 0.87 (s, 3H), 0.70 (s, 3H), 0.61 (s, 3H), 0.49 (s, 3H).

Dimethylsilyl (3-(sec-butyl)-indenyl) (1,5,6,7-tetrahydro-s-indacenyl) Zirconium Dichloride

(3-(Sec-butyl)-1H-inden-1-yl)dimethyl(1,5,6,7-tetrahydro-s-indacen-1-yl)silane

To a stirring solution of (3-sec-butyl-1H-inden-1-yl)dimethylsilyl trifluoromethanesulfonate (5.002 g, 11.72 mmol) in diethyl ether (20 mL), lithium 1,5,6,7-tetrahydro-s-indacenide (1.901 g, 11.72 mmol, 1 eq) was added with diethyl ether (10 mL). The reaction was stirred at room temperature for 26 minutes. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (3×20 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to give a yellow oil. The oil was purified by silica gel column chromatography to afford the product as a pale yellow oil (3.260 g).

Lithium 1-((3-(sec-butyl)-1H-inden-1-id-1-yl)dimethylsilyl)-1,5,6,7-tetrahydro-s-indacen-1-ide

To a stirring solution of (3-(sec-butyl)-1H-inden-1-yl)dimethyl(1,5,6,7-tetrahydro-s-indacen-1-yl)silane (3.260 g, 7.95 mmol) in diethyl ether (20 mL), n-butyllithium (6.4 mL, 2.5M in hexanes, 16.00 mmol, 2.01 eq) was added. The reaction was stirred at room temperature for 11 minutes. The reaction was concentrated under a stream of nitrogen and then under high vacuum to afford the product as an off-white foam, containing diethyl ether (1.42 eq) and hexane (0.02 eq) (4.490 g).

Dimethylsilyl (3-(sec-butyl)-indenyl) (1,5,6,7-tetrahydro-s-indacenyl) Zirconium Dichloride

To a precooled, stirring solution of lithium 1-((3-(sec-butyl)-1H-inden-1-id-1-yl)dimethylsilyl)-1,5,6,7-tetrahydro-s-indacen-1-ide (4.490 g, 7.62 mmol) in toluene (20 mL), zirconium(IV) chloride (1.775 g, 7.62 mmol, 1 eq) was added with toluene (10 mL). The reaction was stirred at room temperature for 15h. The reaction was filtered over Celite. The filtered solid was extracted with additional toluene (2×5 mL). The combined toluene extracts were concentrated under high vacuum at 25° C. to give a brown-orange solid. The solid was stirred in hexane. The resulting suspension was filtered on a plastic fritted funnel. The filtered solid was washed additionally with hexane (3×3 mL). The solid was collected and concentrated under high vacuum to give an orange solid. The solid was stirred in dichloromethane (3 mL). Hexane (15 mL) was added. The resulting suspension was filtered on a plastic frit and washed with hexane (5 mL). The solid was collected and concentrated under high vacuum to afford a fraction of the product as an orange solid (1.648 g, 39%, ratio of 4.0:2.7:1.0:2.5 isomers A, B, C, and D, respectively; used in the polymerization example). Separately, the original toluene washed crude solid was extracted with dichloromethane (20 mL, then 10 mL). The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum. The dichloromethane extract was dissolved in minimal dichloromethane (2 mL). Hexane (10 mL) was added to the solution, resulting in a suspension. The hexane-dichloromethane supernatant was separated from the precipitate, and the precipitate was concentrated under high vacuum to afford another fraction of an orange solid (0.203 g, 4%, ratio of 1.2:1.0:10.6:6.3 isomers A, B, C, and D, respectively). ¹H NMR (400 MHz, CD₂Cl₂): δ 7.58-6.87 (m, 24H), 6.86 (dd, 1H, J=3.3, 0.9 Hz), 6.83 (dd, 1H, J=3.2, 0.9 Hz), 6.67 (dd, 1H, J=3.3, 0.9 Hz), 6.65 (dd, 1H, J=3.2, 0.8 Hz), 6.11 (d, 1H, J=3.3 Hz), 6.09 (d, 1H, J=3.2 Hz), 6.06 (d, 1H, J=3.3 Hz), 6.01 (s, 1H, isomer A, used for isomer ratio), 6.00 (d, 1H, J=3.3 Hz), 5.94 (s, 1H, isomer B, used for isomer ratio), 5.91 (s, 1H, isomer C, used for isomer ratio), 5.81 (s, 1H, isomer D, used for isomer ratio), 3.19-2.68 (m, 20H), 2.10-1.90 (m, 8H), 1.87-1.20 (m, 23H), 1.15 (s, 3H), 1.11 (s, 3H), 1.07 (s, 3H), 1.05 (s, 3H), 0.96 (s, 3H), 0.96-0.91 (m, 6H), 0.89-0.79 (m, 9H), 0.76 (t, 3H, J=7.4 Hz).

Dimethylsilyl (3-isopropyl-1,5,6,7-tetrahydro-s-indacenyl) (1,5,6,7-tetrahydro-s-indacenyl) Zirconium Dichloride

(3-Isopropyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethyl(1,5,6,7-tetrahydro-s-indacen-1-yl)silane

To a stirring solution of (3-isopropyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethylsilyl trifluoromethanesulfonate (0.731 g, 1.20 mmol) in diethyl ether (5 mL), lithium 1,5,6,7-tetrahydro-s-indacenide (0.236 g, 1.18 mmol, 0.99 eq) was added with diethyl ether (10 mL). The reaction was stirred at room temperature for 3h. Then, additional lithium 1,5,6,7-tetrahydro-s-indacenide (0.246 g, 1.23 mmol, 1.03 eq) was added. The reaction was stirred at room temperature for 19h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (2×20 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to afford the product as a yellow oil (0.463 g).

Dimethylsilyl (3-isopropyl-1,5,6,7-tetrahydro-s-indacenyl) (1,5,6,7-tetrahydro-s-indacenyl) Zirconium Dichloride

To a stirring solution of (3-isopropyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethyl(1,5,6,7-tetrahydro-s-indacen-1-yl)silane (0.463 g, 1.13 mmol) in diethyl ether (20 mL), n-butyllithium (0.91 mL, 2.5M in hexanes, 2.28 mmol, 2.02 eq) was added. The reaction was stirred at room temperature for 2h. The reaction was concentrated under a stream of nitrogen and then under high vacuum to give an off-white solid. Diethyl ether (20 mL) was added to the solid, and the solution was stirred. Then, zirconium(IV) chloride (0.263 g, 1.13 mmol, 1 eq) was added. The reaction as stirred at room temperature for 19h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane (10 mL, then 5 mL) and filtered over Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum to give a dark red foam. The foam was stirred in hexane (5 mL), generating an orange suspension. The suspension was allowed to settle. The hexane extract was collected and cooled to −35° C. The cold hexane extract was collected and concentrated under a stream of nitrogen and then under high vacuum. The extract was washed with cold pentane (1 mL) and pentane (2×1 mL) and concentrated under high vacuum to afford the product as an orange solid (0.078 g, 12%, ratio of 1:2 isomers A and B). ¹H NMR (400 MHz, CDCl₃): δ 7.43-7.40 (m, 2H), 7.37-7.32 (m, 4H), 7.19 (br s, 1H), 7.15 (br s, 1H), 6.85 (dd, 1H, J=3.3, 0.9 Hz), 6.69 (dd, 1H, J=3.3, 0.9 Hz), 6.06 (d, 1H, J=3.2 Hz), 5.93 (d, 1H, J=3.3 Hz), 5.86 (s, 1H, isomer B, used for isomer ratio), 5.71 (s, 1H, isomer A, used for isomer ratio), 3.32-3.11 (m, 2H), 3.08-2.60 (m, 16H), 2.16-1.87 (m, 8H), 1.30-1.24 (m, 9H), 1.16 (d, 3H, J=7.0 Hz), 1.12 (s, 3H), 1.04 (s, 3H), 0.91 (s, 3H), 0.90 (d, 3H, J=5.0 Hz).

Dimethylsilyl (3-(sec-butyl)-1,5,6,7-tetrahydro-s-indacenyl) (1,5,6,7-tetrahydro-s-indacenyl) Zirconium Dichloride

(3-(Sec-butyl)-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethyl(1,5,6,7-tetrahydro-s-indacen-1-yl)silane

To a stirring solution of (3-(sec-butyl)-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethylsilyl trifluoromethanesulfonate (4.235 g, 9.93 mmol) in diethyl ether (50 mL), lithium 1,5,6,7-tetrahydro-s-indacenide (1.610 g, 9.93 mmol, 1 eq) was added with diethyl ether (20 mL). The reaction was stirred at room temperature overnight. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (3×20 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum. The crude was purified by silica gel column chromatography to afford the product as an off-white solid (2.177 g).

Lithium 3-(sec-butyl)-1-((6,7-dihydro-s-indacen-1-id-1(5H)-yl)dimethylsilyl)-1,5,6,7-tetrahydro-s-indacen-1-ide

To a stirring solution of (3-(sec-butyl)-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethyl(1,5,6,7-tetrahydro-s-indacen-1-yl)silane (2.177 g, 5.13 mmol) in diethyl ether (40 mL), n-butyllithium (4.1 mL, 2.5M in hexanes, 10.25 mmol, 2 eq) was added. The reaction was stirred at room temperature for 16h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was washed with hexane (20 mL) and concentrated under high vacuum to afford the product as an off-white solid, containing diethyl ether (0.64 eq) (2.420 g).

Dimethylsilyl (3-(sec-butyl)-1,5,6,7-tetrahydro-s-indacenyl) (1,5,6,7-tetrahydro-s-indacenyl) Zirconium Dichloride

To a stirring suspension of zirconium(IV) chloride (1.165 g, 5.00 mmol, 1 eq) in toluene (20 mL), a suspension of lithium 3-(sec-butyl)-1-((6,7-dihydro-s-indacen-1-id-1(5H)-yl)dimethylsilyl)-1,5,6,7-tetrahydro-s-indacen-1-ide (2.420 g, 5.00 mmol) in toluene (50 mL) was added. The reaction was stirred at room temperature for 4.5h. The reaction was filtered over Celite. The filtered solid was further extracted with toluene (2×10 mL). The combined toluene extracts were concentrated under high vacuum at 30° C. The residue was washed with hexane and concentrated under high vacuum. Separately, the toluene washed crude was extracted with dichloromethane. The dichloromethane extract was concentrated under a stream of nitrogen and then under high vacuum. The dichloromethane extract was washed with hexane and concentrated under a stream of nitrogen and then under high vacuum. The hexane washed dichloromethane extract and the hexane washed toluene extract were combined to afford the product as an orange solid (1.501 g, 51%, ratio of 1.0:1.1:1.1:2.1 isomers A, B, C, and D). ¹H NMR (400 MHz, CD₂Cl₂): δ 7.41-7.15 (m, 16H), 6.81 (d, 1H, J=3.4 Hz), 6.79 (d, 1H, J=3.2 Hz), 6.65 (d, 1H, J=3.3 Hz), 6.63 (d, 1H, J=3.2 Hz), 6.08 (d, 1H, J=3.3 Hz, isomer A, used for isomer ratio), 6.06 (d, 1H, J=3.2 Hz, isomer D, used for isomer ratio), 6.00 (d, 1H, J=3.4 Hz, isomer B, used for isomer ratio), 5.94 (d, 1H, J=3.3 Hz, isomer C, used for isomer ratio), 5.92 (s, 1H), 5.86 (s, 1H), 5.79 (s, 1H), 5.69 (s, 1H), 3.81-3.60 (m, 4H), 3.14-2.61 (m, 32H), 2.21-1.90 (m, 16H), 1.86-0.71 (m, 56H).

Dimethylsilyl (indenyl) (3-(sec-butyl)-indenyl) Zirconium Dichloride

(3-(Sec-butyl)-1H-inden-1-yl)(1H-inden-1-yl)dimethylsilane

To a stirring solution of (3-(sec-butyl)-1H-inden-1-yl)dimethylsilyl trifluoromethanesulfonate (2.190 g, 5.79 mmol) in diethyl ether (60 mL), lithium indenide (0.706 g, 5.78 mmol, 1 eq) was added, washing with diethyl ether (10 mL). The reaction was stirred at room temperature for 25h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (2×20 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to afford the product as an oil (1.840 g).

Lithium 1-((1H-inden-1-id-1-yl)dimethylsilyl)-3-(sec-butyl)-1H-inden-1-ide

To a stirring solution of (3-(sec-butyl)-1H-inden-1-yl)(1H-inden-1-yl)dimethylsilane (1.840 g, 5.34 mmol) in diethyl ether (20 mL), n-butyllithium (4.3 mL, 2.5M in hexanes, 10.76 mmol, 2.01 eq) was added. The reaction was stirred at room temperature for 41 minutes. The reaction was concentrated under a stream of nitrogen and then under high vacuum to afford the product as an orange solid, containing diethyl ether (0.59 eq) and hexane (0.42 eq) (2.355 g).

Dimethylsilyl (indenyl) (3-(sec-butyl)-indenyl) Zirconium Dichloride

To a stirring solution of lithium 1-((1H-inden-1-id-1-yl)dimethylsilyl)-3-(sec-butyl)-1H-inden-1-ide (2.355 g, 5.40 mmol) in toluene (20 mL), zirconium(IV) chloride (1.262 g, 5.42 mmol, 1 eq) was added with toluene (10 mL). The reaction was stirred at room temperature for 7h. The reaction was filtered over Celite. The filtered solid was further extracted with toluene (2×10 mL). The combined toluene extracts were concentrated under high vacuum at 35° C. The residue was washed with pentane (3×10 mL) and filtered on a plastic frit. The solid was collected and concentrated under high vacuum to afford the product as a red-orange solid (1.861 g, 68%, ratio of 1.0:1.1:1.3:1.4 isomers A, B, C, and D). ¹H NMR (400 MHz, CD₂Cl₂): δ 7.67-6.87 (m, 34H), 6.82 (dd, 1H, J=3.3, 0.9 Hz), 6.78 (dd, 1H, J=3.2, 0.9 Hz), 6.18 (d, 1H, J=3.3 Hz), 6.17 (d, 1H, J=3.2 Hz), 6.15 (d, 1H, J=3.3 Hz), 6.09 (d, 1H, J=3.3 Hz), 5.97 (s, 1H, isomer D, used for isomer ratio), 5.93 (s, 1H, isomer C, used for isomer ratio), 5.89 (s, 1H, isomer A, used for isomer ratio), 5.82 (s, 1H, isomer B, used for isomer ratio), 3.20-3.10 (m, 1H), 3.09-2.96 (m, 2H), 2.92-2.82 (m, 1H), 1.86-0.72 (m, 56H).

Dimethylsilyl (4-(o-biphenyl)-indenyl) (3-(2-pentyl)-1,5,6,7-tetrahydro-s-indacenyl) Zirconium Dichloride

(4-([1,1′-Biphenyl]-2-yl)-1H-inden-1-yl)dimethyl(3-(pentan-2-yl)-1,5,6,7-tetrahydro-s-indacen-1-yl)silane

To a stirring solution of dimethyl(3-(pentan-2-yl)-1,5,6,7-tetrahydro-s-indacen-1-yl)silyl trifluoromethanesulfonate (3.342 g, 7.73 mmol) in diethyl ether (20 mL), a solution of lithium 4-([1,1′-biphenyl]-2-yl)-1H-inden-1-ide (2.290 g, 7.73 mmol, 1 eq) in diethyl ether (10 mL) was added. The reaction was stirred at room temperature for 15h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with hexane (2×20 mL) and filtered over Celite. The combined hexane extracts were concentrated under a stream of nitrogen and then under high vacuum to afford the product as a pink foam, containing hexane (0.35 eq) (4.544 g).

Lithium 1-((4-([1,1′-biphenyl]-2-yl)-1H-inden-1-id-1-yl)dimethylsilyl)-3-(pentan-2-yl)-1,5,6,7-tetrahydro-s-indacen-1-ide

To a stirring solution of (4-([1,1′-biphenyl]-2-yl)-1H-inden-1-yl)dimethyl(3-(pentan-2-yl)-1,5,6,7-tetrahydro-s-indacen-1-yl)silane (4.544 g, 7.82 mmol) in diethyl ether (40 mL), n-butyllithium (6.3 mL, 2.5M in hexanes, 15.75 mmol, 2.01 eq) was added. The reaction was stirred at room temperature for 50 minutes. The reaction was concentrated under a stream of nitrogen and then under high vacuum to afford the product as an orange-yellow foam, containing diethyl ether (1.50 eq) and hexane (0.98 eq) (5.491 g).

Dimethylsilyl (4-(o-biphenyl)-indenyl) (3-(2-pentyl)-1,5,6,7-tetrahydro-s-indacenyl) Zirconium Dichloride

To a stirring suspension of zirconium(IV) chloride (1.688 g, 7.24 mmol, 1 eq) in toluene (20 mL), a solution of lithium 1-((4-([1,1′-biphenyl]-2-yl)-1H-inden-1-id-1-yl)dimethylsilyl)-3-(pentan-2-yl)-1,5,6,7-tetrahydro-s-indacen-1-ide (5.491 g, 7.24 mmol) in toluene (20 mL) was added. The reaction was stirred at room temperature for 18.5h. The reaction was filtered over Celite. The filtrate was concentrated under high vacuum at 30° C. to give a brown foam. The foam was stirred in hexane (20 mL). The resulting suspension was filtered over Celite. The hexane filtrate was concentrated under a stream of nitrogen and then under high vacuum. The residue was dissolved in diethyl ether (2 mL), and the resulting solution was diluted with pentane (to 20 mL total). The solid was allowed to settle, and the diethyl ether-pentane supernatant was separated from the precipitate. The diethyl ether-pentane extract was partially concentrated until the cooling led to the precipitation of orange solid. The cold diethyl ether-pentane supernatant was removed, and the precipitate remaining was concentrated under high vacuum. The precipitate was dissolved in diethyl ether and mixed with the diethyl ether-pentane washed hexane extract of the toluene extract, and the combined solution was concentrated under a stream of nitrogen and then under high vacuum to afford the product as an orange powder (1.526 g, 29%, ratio of 1:1:1:1 isomers A, B, C, and D). ¹H NMR (400 MHz, C₆D₆): δ 8.30-8.15 (m, 4H), 7.50-6.62 (m, 56H), 5.86 (d, 1H, J=3.4 Hz), 5.85 (s, 1H), 5.84 (d, 1H, J=3.3 Hz), 5.78 (s, 1H), 5.64 (s, 1H), 5.60-5.57 (m, 2H), 5.55 (br d, 1H, J=3.2 Hz), 3.48-3.30 (m, 4H), 2.94-2.54 (m, 16H), 1.90-1.18 (m, 36H), 0.97-0.73 (m, 18H), 0.57 (s, 3H), 0.56 (s, 6H), 0.55 (s, 3H), 0.41 (s, 3H), 0.35 (s, 3H). ¹H NMR (400 MHz, CD₂Cl₂) (region 6.0-5.6 ppm used for determination of isomer ratio): δ 5.97 (d, 1H, J=3.3 Hz), 5.92 (d, 2H, J=3.4 Hz), 5.88 (d, 1H, J=3.3 Hz), 5.84 (s, 1H, isomer A, used for isomer ratio), 5.77 (s, 1H, isomer B, used for isomer ratio), 5.74 (s, 1H, isomer C, used for isomer ratio), 5.65 (s, 1H, isomer D, used for isomer ratio).

General Supportation Procedure

SMAO, Also Referred to as SMAO-ES70-875:

Methylalumoxane treated silica was prepared in a manner similar to the following.

In a 4 L stirred vessel in a drybox methylalumoxane (MAO, 30 wt % in toluene, approx. 1000 grams) is added along with approx. 2000 g of toluene. This solution is then stirred at 60 RPM for 5 minutes. Next, approx. 800 grams of ES-70-875 silica is added to the vessel. This slurry is then heated at 100° C. and stirred at 120 RPM for 3 hours. The temperature is then reduced to 25° C. and cooled to temperature over 2 hours. Once cooled, the vessel is set to 8 RPM and placed under vacuum for 72 hours. After emptying the vessel and sieving the supported MAO, approximately 1100 g of supported MAO will be collected.

ES-70-875 silica is ES70™ silica (PQ Corporation, Conshohocken, Pennsylvania) that has been calcined at approximately 875° C. Typically, the ES70™ silica is calcined at 880° C. for four hours after being ramped to 880° C. according to the following ramp rates:

° C. ° C./h ° C. ambient 100 200 200 50 300 300 133 400 400 200 800 800 50 880

For each sample, the desired amount of catalyst (40 μmol catalyst/g SMAO) was transferred to a 20 mL glass vial. Then, toluene (about 3 g) was added. Finally, SMAO (0.5 g) was added. The contents of the vial were mixed (60-90 minutes) on a shaker. The contents of the vial were allowed to settle. The supernatant was decanted into solvent waste. If necessary, the remnants of each vial were stored in a freezer (−35° C.) until needed.

The vials were uncapped and loaded into the sample trays in a SpeedVac. The SpeedVac was set to run at 45° C. for 45 min at 0.1 vacuum setting. Once complete, the vials were removed, and the powder contents of each vial were poured into a separate pre-weighed 4 mL vial. The vials were capped, sealed with electrical tape, and stored in the dry box freezer for future use.

Catalyst C (comparative) was a DAVISON 948 silica supported catalyst made in a manner analogous to that described in U.S. Pat. No. 6,180,736 using the (1-Me-3-nBuCp)₂ZrC1₂ metallocene (metallocene 3).

General Procedure for High Throughput Ethylene/1-Hexene Polymerization and Polymer Characterization (Tables 3 and 4)

Unless stated otherwise ethylene homopolymerization and ethylene-hexene copolymerizations are carried out in a parallel pressure reactor, as generally described in U.S. Pat. Nos. 6,306,658; 6,455,316; WO 00/09255; and Murphy et al., J. Am. Chem. Soc., 2003, Vol. 125, pp. 4306-4317, each of which is incorporated by reference herein in its entirety. Although specific quantities, temperatures, solvents, reactants, reactants ratios, pressures, and other variables may need to be adjusted from one reaction to the next, the following describes a typical polymerization performed in a parallel, pressure reactor.

Preparation of catalyst slurry for high throughput run: In a dry box, 45 mg of supported catalyst is weighed into a 20 mL glass vial. 15 mL of toluene is added to the vial to make a slurry that contained 3 mg supported catalyst/mL slurry. The resulting mixture is vortexed prior to injection.

Starting material preparations: Solvents, polymerization grade toluene and isohexane are supplied by ExxonMobil Chemical Company and thoroughly dried and degassed prior to use. Polymerization grade ethylene is used and further purified by passing it through a series of columns: 500 cc Oxyclear cylinder from Labclear (Oakland, Calif.) followed by a 500 cc column packed with dried 3 Å mole sieves purchased from Aldrich Chemical Company, and a 500 cc column packed with dried 5 Å mole sieves purchased from Aldrich Chemical Company.

TnOA1 (tri-n-octylaluminum, neat) is used as a 2 mmol/L solution in toluene.

Polymerizations are conducted in an inert atmosphere (N₂) drybox using autoclaves equipped with an external heater for temperature control, glass inserts (internal volume of reactor=22.5 mL), septum inlets, regulated supply of nitrogen, ethylene and hexene, and equipped with disposable PEEK mechanical stirrers (800 RPM). The autoclaves are prepared by purging with dry nitrogen prior to use.

Ethylene/1-hexene Copolymerization

The reactor is prepared as described above, and then purged with ethylene. Isohexane, 1-hexene and TnOA1 are added via syringe at room temperature and atmospheric pressure. The reactor is then brought to process temperature (85° C.) and charged with ethylene to process pressure (130 psig=896 kPa) while stirring at 800 RPM. The transition metal compound “TMC” (100 aL of a 3 mg/mL toluene slurry, unless indicated otherwise) is added via syringe with the reactor at process conditions. TnOA1 is used as 200 aL of a 20 mmol/L in isohexane solution. Amounts of reagents not specified above are given in Table 1. No other reagent is used. Ethylene is allowed to enter (through the use of computer controlled solenoid valves) the autoclaves during polymerization to maintain reactor gauge pressure (+/−2 psig). Reactor temperature is monitored and typically maintained within +/−1° C. Polymerizations are halted by addition of approximately 50 psi O₂/Ar (5 mol % O₂) gas mixture to the autoclaves for approximately 30 seconds. The polymerizations are quenched after a predetermined cumulative amount of ethylene had been added or for a maximum of 45 minutes polymerization time. In addition to the quench time for each run, the reactors are cooled and vented. The polymer is isolated after the solvent is removed in-vacuo. Yields reported include total weight of polymer and residual catalyst. The resultant polymer is analyzed by Rapid GPC to determine the molecular weight and by DSC to determine the melting point.

GPC, 1-Hexene Incorporation, and DSC Measurements

To determine various molecular weight related values of the high throughput samples by GPC, high temperature size exclusion chromatography was performed using an automated “Rapid GPC” system. This apparatus has a series of three 30 cm×7.5 mm linear columns, each containing PLgel 10 um, Mix B. The GPC system was calibrated using polystyrene standards ranging from 580-3,390,000 g/mol. The system was operated at an eluent flow rate of 2.0 mL/minutes and an oven temperature of 165° C. 1,2,4-trichlorobenzene was used as the eluent. The polymer samples were dissolved in 1,2,4-trichlorobenzene at a concentration of 0.1-0.9 mg/mL. 250 uL of a polymer solution was injected into the system. The concentration of the polymer in the eluent was monitored using a Polymer Char IR4 detector. The molecular weights presented are relative to linear polystyrene standards and are uncorrected.

The amount of hexene incorporated in the polymers (wt %) was estimated by rapid FT-IR spectroscopy on a Bruker Vertex 70 IR in reflection mode. Samples were prepared in a thin film format by evaporative deposition techniques. Weight percent hexene was obtained from the ratio of peak heights in the ranges of 1377-1382 cm⁻¹ to 4300-4340 cm⁻¹. This method was calibrated using a set of ethylene hexene copolymers with a range of known wt % hexene content.

Differential Scanning Calorimetry (DSC) measurements (DSC-Procedure-1) were performed on a TA-Q200 instrument to determine the melting point of the polymers. Samples were pre-annealed at 220° C. for 15 minutes and then allowed to cool to room temperature overnight. The samples were then heated to 220° C. at a rate of 100° C./minutes and then cooled at a rate of 50° C./min. Melting points were collected during the heating period.

General Procedure-1 for Polymerization in Gas Phase Autoclave Reactor (Table 5)

A 2 Liter Autoclave reactor (Parker Autoclave Engineers Research Systems) is heated to 105° C. under a continuous purge of anhydrous nitrogen gas (˜2-5 SLPM) for 60 minutes to reduce residual oxygen and moisture. Anhydrous sodium chloride, 50-400 g (Fisher, oven-dried 48 hr at 180° C., stored under inert atmosphere in glovebox), is loaded into a 0.5 L Whitey cylinder and charged to the reactor with nitrogen pressure. Reactor is maintained at 105° C. with continued nitrogen purge for 30 minutes. A solid scavenger (5.0 g, SMAO-ES70-875 is loaded to a Whitey sample cylinder and added to the reactor with nitrogen charge. Nitrogen purge is discontinued and the reactor maintained at 105° C. and 70 psig N₂ as impeller rotates the bed for 30 min (100-200 RPM). The reactor is adjusted to desired reactor temperature (60° C.-100° C.) and the nitrogen pressure reduced to ca. 20 psig. Comonomer (1-4 mL of 1-butene, 1-hexene, or 1-octene) is charged into the reactor from a syringe pump (Teledyne Isco), followed with 50-500 mL of 10% hydrogen gas (nitrogen balance). Reactor is subsequently pressurized with ethylene monomer to a total pressure of 240 psig. Quantities of comonomer and hydrogen are monitored by gas chromatography and adjusted to desired gas phase ratios of comonomer/ethylene and hydrogen/ethylene.

Solid Catalyst (5.0-100.0 mg, MAO-silica support) is loaded into a small injection tube under inert atmosphere nitrogen in a glovebox. The catalyst injection tube is attached to the reactor and catalyst is quickly charged into reactor with high pressure nitrogen (300-350 psig), and polymerization is monitored for the desired reaction time (30-300 min). The comonomer and hydrogen are continuously added with mass flow controllers to maintain specific concentrations during the polymerization, as measured by GC. Ethylene monomer is continuously added, maintaining a constant total reactor pressure of 300-350 psig (constant C₂ partial pressure of 200-220 psig). After the desired reaction time (1 hour), the reactor is vented and cooled to ambient pressure and temperature. The reaction product is collected, dried 60-90 min under nitrogen purge, and weighed for crude yield. The product is transferred to a standard 2 L beaker and washed with 3×2000 mL of distilled water with rapid magnetic stirring to remove sodium chloride and residual silica. Polymer is collected by filtration and oven dried under vacuum at 40° C. for 12 hr, then weight is measured for final isolated yield. Polymer is analyzed by thermogravimetric analysis to ensure ≤1 wt % residual inorganic material, then is subsequently characterized by standard ASTM methods for density and molecular weight behavior.

General Procedure-2 for Polymerization in Gas Phase Autoclave Reactor (Table 8)

A 2 Liter Autoclave reactor (Parker Autoclave Engineers Research Systems) is filled with 200-400 grams of granular NaCl. The salt is agitated (100-200 RPM of impeller rotation speed) and heated to a temperature above 100° C. under a continuous purge of house nitrogen gas for 60 minutes. This reduces the residual oxygen and moisture within the reactor and salt bed. A solid scavenger (4.0-6.0 g, SMAO-ES70-875) is loaded into a Whitey sample cylinder and added to the reactor with nitrogen charge. The reactor is adjusted to the desired reactor temperature (50° C.-100° C.) and ambient pressure. The desired amount of 25% hydrogen gas (nitrogen balance) is loaded into the reactor using a Brooks Mass Flow Controller. Then, a specified amount of Iso-pentane is added using a Whitey sample cylinder and injected with high pressure nitrogen. Using a ratio control, the Comonomer (1-butene, 1-hexene, or 1-octene) is pushed into the reactor from a syringe pump (Teledyne Isco) while ethylene is filling the reactor to a total pressure of about 240 psig. Solid Catalyst is loaded into a small injection tube under inert atmosphere nitrogen in a glovebox. The catalyst injection tube is attached to the reactor and catalyst is quickly charged into reactor with high pressure nitrogen up to 300-350 psig, and polymerization is monitored for the desired reaction time (30-90 min). Ethylene monomer is continuously added, maintaining a constant total reactor pressure of 300-350 psig. Nitrogen is continuously injected to maintain a constant ethylene partial pressure. The comonomer and hydrogen are continuously added and adjusted to maintain desired gas phase ratios of comonomer/ethylene and hydrogen/ethylene, as monitored by gas chromatography. After the desired reaction time, the reactor is vented and cooled to ambient pressure and temperature. The reaction product is collected and weighed for an approximate yield. The product is transferred to a standard 4 L beaker with 2000 mL of distilled water and soap. The solution is rapidly agitated using a magnetic stirring plate and stir bar for the desired time. The solution is then transferred to a separator funnel and then allowed to settle. The heavy particles that have fallen to the bottom of the solution are washed out. The polymer is washed until the remaining water is clear of particles. The polymer is collected by filtration flask, oven dried at 100° C. overnight, and then weight is measured for final isolated yield. Afterwards, polymer is characterized by standard ASTM methods for density and Melt Index, as well as other analytical tests.

GPC 4D Procedure: Molecular Weight, Comonomer Composition and Long Chain Branching Determination by GPC-IR Hyphenated with Multiple Detectors

Unless otherwise indicated, the distribution and the moments of molecular weight (Mw, Mn, Mw/Mn, etc.), the comonomer content (C₂, C₃, C₆, etc.) and the branching index (g′_(vis)) are determined by using a high temperature Gel Permeation Chromatography (Polymer Char GPC-IR) equipped with a multiple-channel band-filter based Infrared detector IR5, an 18-angle light scattering detector and a viscometer. Three Agilent PLgel 10-μm Mixed-B LS columns are used to provide polymer separation. Aldrich reagent grade 1,2,4-trichlorobenzene (TCB) with 300 ppm antioxidant butylated hydroxytoluene (BHT) is used as the mobile phase. The TCB mixture is filtered through a 0.1-μm Teflon filter and degassed with an online degasser before entering the GPC instrument. The nominal flow rate is 1.0 ml/min and the nominal injection volume is 200 μL. The whole system including transfer lines, columns, and detectors are contained in an oven maintained at 145° C. The polymer sample is weighed and sealed in a standard vial with 80-μL flow marker (Heptane) added to it. After loading the vial in the autosampler, polymer is automatically dissolved in the instrument with 8 ml added TCB solvent. The polymer is dissolved at 160° C. with continuous shaking for about 1 hour for most PE samples or 2 hour for PP samples. The TCB densities used in concentration calculation are 1.463 g/ml at room temperature and 1.284 g/ml at 145° C. The sample solution concentration is from 0.2 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples. The concentration (c), at each point in the chromatogram is calculated from the baseline-subtracted IR5 broadband signal intensity (I), using the following equation: c=βI, where β is the mass constant. The mass recovery is calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume. The conventional molecular weight (IR MW) is determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards ranging from 700 to 10M gm/mole. The MW at each elution volume is calculated with following equation:

${\log\; M} = {\frac{\log\left( {K_{PS}/K} \right)}{a + 1} + {\frac{a_{PS} + 1}{a + 1}\log\; M_{PS}}}$ where the variables with subscript “PS” stand for polystyrene while those without a subscript are for the test samples. In this method, α_(PS)=0.67 and K_(PS)=0.000175 while α and K are for other materials as calculated and published in literature (Sun, T. et al. Macromolecules, 2001, 34, 6812), except that for purposes of the present disclosure, α=0.695 and K=0.000579 for linear ethylene polymers, α=0.705 and K=0.0002288 for linear propylene polymers, α=0.695 and K=0.000181 for linear butene polymers, α is 0.695 and K is 0.000579*(1−0.0087*w2b+0.000018*(w2b){circumflex over ( )}2) for ethylene-butene copolymer where w2b is a bulk weight percent of butene comonomer, α is 0.695 and K is 0.000579*(1−0.0075*w2b) for ethylene-hexene copolymer where w2b is a bulk weight percent of hexene comonomer, and α is 0.695 and K is 0.000579*(1−0.0077*w2b) for ethylene-octene copolymer where w2b is a bulk weight percent of octene comonomer. Concentrations are expressed in g/cm³, molecular weight is expressed in g/mole, and intrinsic viscosity (hence K in the Mark-Houwink equation) is expressed in dL/g unless otherwise noted.

The comonomer composition is determined by the ratio of the IR5 detector intensity corresponding to CH₂ and CH₃ channel calibrated with a series of PE and PP homo/copolymer standards whose nominal value are predetermined by NMR or FTIR. In particular, this provides the methyls per 1000 total carbons (CH₃/1000TC) as a function of molecular weight. The short-chain branch (SCB) content per 1000TC (SCB/1000TC) is then computed as a function of molecular weight by applying a chain-end correction to the CH₃/1000TC function, assuming each chain to be linear and terminated by a methyl group at each end. The weight % comonomer is then obtained from the following expression in which ƒ is 0.3, 0.4, 0.6, 0.8, and so on for C3, C4, C6, C8, and so on co-monomers, respectively. w2=ƒ*SCB/1000TC

The bulk composition of the polymer from the GPC-IR and GPC-4D analyses is obtained by considering the entire signals of the CH₃ and CH₂ channels between the integration limits of the concentration chromatogram. First, the following ratio is obtained

${{Bulk}\mspace{14mu}{IR}\mspace{14mu}{ratio}} = {\frac{{Area}\mspace{14mu}{of}\mspace{14mu}{CH}_{3}\mspace{14mu}{signal}\mspace{14mu}{within}\mspace{14mu}{integration}\mspace{14mu}{limits}}{{Area}\mspace{14mu}{of}\mspace{14mu}{CH}_{2}\mspace{14mu}{signal}\mspace{14mu}{within}\mspace{14mu}{integration}\mspace{14mu}{limits}}.}$

Then the same calibration of the CH₃ and CH₂ signal ratio, as mentioned previously in obtaining the CH3/1000TC as a function of molecular weight, is applied to obtain the bulk CH3/1000TC. A bulk methyl chain ends per 1000TC (bulk CH3end/1000TC) is obtained by weight-averaging the chain-end correction over the molecular-weight range. Then

w 2 b = f * bulk  CH 3/1000 TC ${{bulk}\mspace{14mu}{{SCB}/1000}\;{TC}} = {{{bulk}\mspace{14mu}{CH}\;{3/1000}\;{TC}} - {{bulk}\frac{{CH}\; 3\;{end}}{1000\;{TC}}}}$ and bulk SCB/1000TC is converted to bulk w2 in the same manner as described above.

The LS detector is the 18-angle Wyatt Technology High Temperature DAWN HELEOSII. The LS molecular weight (M) at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (Light Scattering from Polymer Solutions; Huglin, M. B., Ed.; Academic Press, 1972.):

$\frac{K_{o}c}{\Delta\;{R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2\; A_{2}{c.}}}$

Here, ΔR(θ) is the measured excess Rayleigh scattering intensity at scattering angle θ, c is the polymer concentration determined from the IR5 analysis, A₂ is the second virial coefficient, P(θ) is the form factor for a monodisperse random coil, and K_(o) is the optical constant for the system:

$K_{o} = \frac{4\;\pi^{2}{n^{2}\left( {{dn}/{dc}} \right)}^{2}}{\lambda^{4}N_{A}}$ where N_(A) is Avogadro's number, and (dn/dc) is the refractive index increment for the system. The refractive index, n=1.500 for TCB at 145° C. and λ=665 nm. For analyzing polyethylene homopolymers, ethylene-hexene copolymers, and ethylene-octene copolymers, dn/dc=0.1048 ml/mg and A₂=0.0015; for analyzing ethylene-butene copolymers, dn/dc=0.1048*(1−0.00126*w2) ml/mg and A₂=0.0015 where w2 is weight percent butene comonomer.

A high temperature Agilent (or Viscotek Corporation) viscometer, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure. The specific viscosity, η_(s), for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [η], at each point in the chromatogram is calculated from the equation [η]=η_(s)/c, where c is concentration and is determined from the IR5 broadband channel output. The viscosity MW at each point is calculated as M=K_(PS)M^(α) ^(PS) ⁺¹/[η], where α_(ps) is 0.67 and K_(ps) is 0.000175.

The branching index (g′_(vis)) is calculated using the output of the GPC-IR5-LS-VIS method as follows. The average intrinsic viscosity, [η]_(avg), of the sample is calculated by:

$\left\lfloor \eta \right\rfloor_{avg} = \frac{\sum{c_{i}\lbrack\eta\rbrack}_{i}}{\sum c_{i}}$ where the summations are over the chromatographic slices, i, between the integration limits. The branching index g′_(vis) is defined as

${g_{vis}^{\prime} = \frac{\lbrack\eta\rbrack_{avg}}{{KM}_{v}^{\alpha}}},$ where M_(V) is the viscosity-average molecular weight based on molecular weights determined by LS analysis and the K and α are for the reference linear polymer, which are, for purposes of the present disclosure, α=0.695 and K=0.000579 for linear ethylene polymers, α=0.705 and K=0.0002288 for linear propylene polymers, α=0.695 and K=0.000181 for linear butene polymers, α is 0.695 and K is 0.000579*(1−0.0087*w2b+0.000018*(w2b){circumflex over ( )}2) for ethylene-butene copolymer where w2b is a bulk weight percent of butene comonomer, α is 0.695 and K is 0.000579*(1−0.0075*w2b) for ethylene-hexene copolymer where w2b is a bulk weight percent of hexene comonomer, and a is 0.695 and K is 0.000579*(1-0.0077*w2b) for ethylene-octene copolymer where w2b is a bulk weight percent of octene comonomer. Concentrations are expressed in g/cm³, molecular weight is expressed in g/mole, and intrinsic viscosity (hence K in the Mark-Houwink equation) is expressed in dL/g unless otherwise noted. Calculation of the w2b values is as discussed above.

Experimental and analysis details not described above, including how the detectors are calibrated and how to calculate the composition dependence of Mark-Houwink parameters and the second-virial coefficient, are described by T. Sun, P. Brant, R. R. Chance, and W. W. Graessley (Macromolecules, 2001, Vol. 34(19), pp. 6812-6820).

All molecular weights are weight average unless otherwise noted. All molecular weights are reported in g/mol unless otherwise noted. C₆ wt % is estimated by IR (GPC4D).

Methyl groups per 1000 carbons (CH₃/1000Carbons) and chain saturation is determined by ¹H NMR.

Melt Index (MI, also referred to as 12) is measured according to ASTM D1238 at 190° C., under a load of 2.16 kg unless otherwise noted. The units for MI are g/10 min or dg/min.

High Load Melt Index (HLMI, also referred to as I21) is the melt flow rate measured according to ASTM D-1238 at 190° C., under a load of 21.6 kg. The units for HLMI are g/10 min or dg/min.

Melt Index Ratio (MIR) is the ratio of the high load melt index to the melt index, or I21/I2.

Extensional Rheology Measurements

Strain hardening, also known as extensional thickening, can be described as the resistance of a polymer melt to stretching. It is observed as a steep increase of elongational viscosity at large strain, which deviates from the linear viscoelastic envelope.

Extensional viscosity measurements were performed using a DHR-rheometer from TA Instruments equipped with Sentmanat Extensional Rheometer (SER) fixture at Hencky strain rates: 0.01, 0.1, 1.0, and 10.0 s⁻¹ at temperature of 130° C. or 150° C.

All samples for the extensional rheology measurements have been prepared from granular reactor material using a hot press. Material granules are compressed during 2-5 min at temperatures about 190° C. Through slow cooling in the press stress-free, equilibrated samples are obtained. Homogeneous rectangular plates are cut manually from the compression molded plaque using a razor blade to produce strips with approximate dimensions (18 mm(length)×7 mm(width)×1 mm(thickness)) appropriate for uniaxial extension measurements.

It should be noted that all measurements of stress growth in this study are limited by the design features of the SER fixture. When strain reaches a value of approx. 3.5 strain units the sample starts to overlay on itself thus causing discontinuity of the measured data.

Differential Scanning Calorimetry (DSC-Procedure-2). Melting Temperature, Tm, is measured by differential scanning calorimetry (“DSC”) using a DSCQ200 unit. The sample is first equilibrated at 25° C. and subsequently heated to 180° C. using a heating rate of 10° C./min (first heat). The sample is held at 180° C. for 3 min. The sample is subsequently cooled down to 25° C. with a constant cooling rate of 10° C./min (first cool). The sample is equilibrated at 25° C. before being heated to 180° C. at a constant heating rate of 10° C./min (second heat). The exothermic peak of crystallization (first cool) is analyzed using the TA Universal Analysis software and the corresponding to 10° C./min cooling rate is determined. The endothermic peak of melting (second heat) is also analyzed using the TA Universal Analysis software and the peak melting temperature (Tm) corresponding to 10° C./min heating rate is determined. In the event of conflict between the DSC Procedure-1 and DSC procedure-2, DSC procedure-2 is used.

CFC Procedure

Cross-fractionation chromatography (CFC) analysis was done using a CFC-2 instrument from Polymer Char, S.A., Valencia, Spain. The principles of CFC analysis and a general description of the particular apparatus used are given in the article Ortin, A.; Monrabal, B.; Sancho-Tello, J. Macromol. Symp., 2007, 257, 13. FIG. 1 of the article is an appropriate schematic of the particular apparatus used. Pertinent details of the analysis method and features of the apparatus used are as follows.

The solvent used for preparing the sample solution and for elution was 1,2-Dichlorobenzene (ODCB) which was stabilized by dissolving 2 g of 2,6-bis(1,1-dimethylethyl)-4-methylphenol (butylated hydroxytoluene) in a 4-L bottle of fresh solvent at ambient temperature. The sample to be analyzed (25-125 mg) was dissolved in the solvent (25 ml metered at ambient temperature) by stirring (200 rpm) at 150° C. for 75 min. A small volume (0.5 ml) of the solution was introduced into a TREF column (stainless steel; o.d., ⅜″; length, 15 cm; packing, non-porous stainless steel micro-balls) at 150° C., and the column temperature was stabilized for 30 min at a temperature (120-125° C.) approximately 20° C. higher than the highest-temperature fraction for which the GPC analysis was included in obtaining the final bivariate distribution. The sample volume was then allowed to crystallize in the column by reducing the temperature to an appropriate low temperature (30, 0, or −15° C.) at a cooling rate of 0.2° C./min. The low temperature was held for 10 min before injecting the solvent flow (1 ml/min) into the TREF column to elute the soluble fraction (SF) into the GPC columns (3×PLgel 10 m Mixed-B 300×7.5 mm, Agilent Technologies, Inc.); the GPC oven was held at high temperature (140° C.). The SF was eluted for 5 min from the TREF column and then the injection valve was put in the “load” position for 40 min to completely elute all of the SF through the GPC columns (standard GPC injections). All subsequent higher-temperature fractions were analyzed using overlapped GPC injections wherein at each temperature step the polymer was allowed to dissolve for at least 16 min and then eluted from the TREF column into the GPC column for 3 min. The IR4 (Polymer Char) infrared detector was used to generate an absorbance signal that is proportional to the concentration of polymer in the eluting flow.

The universal calibration method was used for determining the molecular weight distribution (MWD) and molecular-weight averages (M_(n), M_(w), etc.) of eluting polymer fractions. Thirteen narrow molecular-weight distribution polystyrene standards (obtained from Agilent Technologies, Inc.) within the range of 1.5-8200 kg/mol were used to generate a universal calibration curve. Mark-Houwink parameters were obtained from Appendix I of Mori, S.; Barth, H. G. Size Exclusion Chromatography; Springer, 1999. For polystyrene K=1.38×10⁻dl/g and α=0.7; and for polyethylene K=5.05×10⁻⁴ dl/g and α=0.693 were used. For a polymer fraction, which eluted at a temperature step, that has a weight fraction (weight % recovery) of less than 0.5%, the MWD and the molecular-weight averages were not computed; additionally, such polymer fractions were not included in computing the MWD and the molecular-weight averages of aggregates of fractions.

EXAMPLES

The exemplified catalyst compounds below were prepared according to the general method described above. The following conditions were used in polymerization runs for Table 3: isohexane diluent; total reaction volume: 5 mL; polymerization temperature (T_(p)): 85° C.; ethylene partial pressure: 130 psi.

CATALYST COMPOUNDS OF THE EXAMPLES

Each of the exemplary catalyst compounds below is designated using the acronym “MCN” for “metallocene.”

Catalyst compound MCN1 has the structure shown immediately below:

MCN1 was obtained and used as a mixture of four isomers in a 1:2.3:3.3:7.3 ratio.

Catalyst compound MCN2 has the structure shown immediately below:

MCN2 was obtained and used as a mixture of four isomers in a 1:1.3:2.4:3.9 ratio.

Catalyst compound MCN3 (comparative example) has the structure shown immediately below:

MCN3 (mixture of 2 isomers) was obtained from a commercial source.

Catalyst compound MCN4 (comparative example) has the structure shown immediately below:

MCN4 was obtained and used as a mixture of four isomers in a 1:1:2:2 ratio.

Catalyst compound MCN5 (comparative example) has the structure shown immediately below:

MCN5 was obtained and used as a mixture of two isomers in a 1:1.9 ratio.

Catalyst compound MCN6 (comparative example) has the structure shown immediately below:

MCN6 was obtained and used as a mixture of two isomers in a 1:4 ratio.

Catalyst compound MCN7 has the structure shown immediately below:

MCN7 was obtained and used as a mixture of four isomers.

Catalyst compound MCN8 has the structure shown immediately below:

MCN8 was obtained and used as a mixture of four isomers.

Catalyst compound MCN9 has the structure shown immediately below:

MCN9 was obtained and used as a mixture of four isomers.

Catalyst compound MCN10 has the structure shown immediately below:

MCN10 was obtained and used as a mixture of four isomers.

Catalyst compound MCN11 has the structure shown immediately below:

MCN11 was obtained and used as a mixture of four isomers.

Catalyst compound MCN12 has the structure shown immediately below:

MCN12 was obtained and used as a mixture of four isomers.

Catalyst compound MCN13 has the structure shown immediately below:

MCN13 was obtained and used as a mixture of two isomers.

Catalyst compound MCN14 has the structure shown immediately below:

MCN14 was obtained and used as a mixture of two isomers in a 1/1.1 ratio.

Catalyst Compounds of the Examples for Table 7

Preparation of Example Supported Catalysts

Each of the inventive catalyst compounds (MCN's 1, 2, and 7-14, 15-29) and comparative catalyst compounds MCN 4-6) were supported on ES70 silica using similar conditions, as described below. Table 2 summarizes the supported catalysts.

TABLE 2 Supported Catalysts Prepared with Catalyst Compounds Supported Catalyst Catalyst Compound/Silica Catalyst A MCN1/ES70 Catalyst B MCN2/ES70 Catalyst C (comparative) MCN3/DAVIS0N 948 Catalyst D (comparative) MCN4/ES70 Catalyst E (comparative) MCN5/ES70 Catalyst F (comparative) MCN6/ES70 Catalyst G MCN7/ES70 Catalyst H MCN8/ES70 Catalyst I MCN9/ES70 Catalyst J MCN10/ES70 Catalyst K MCN11/ES70 Catalyst L MCN12/ES70 Catalyst M MCN13/ES70 Catalyst N MCN14/ES70 Catalyst O MCN15/ES70 Catalyst P MCN16/ES70 Catalyst Q MCN17/ES70 Catalyst R MCN18/ES70 Catalyst S MCN19/ES70 Catalyst T MCN20/ES70 Catalyst U MCN21/ES70 Catalyst V MCN22/ES70 Catalyst W MCN23/ES70 Catalyst X MCN24/ES70 Catalyst Y MCN25/ES70 Catalyst Z MCN26/ES70 Catalyst AA MCN27/ES70 Catalyst AB MCN28/ES70 Catalyst AC MCN29/ES70 General Supportation Procedure

All manipulations were carried out in a glove box under nitrogen or argon. For each sample, the desired amount of catalyst (40 μmol catalyst/g SMAO) was transferred to a 20 mL glass vial. Then, toluene (about 3 g) was added. Finally, SMAO (0.5 g) was added. The vial was sealed with a Teflon cap, and the contents of the vial were vortexed (>90 minutes) on a shaker. The contents of the vial were allowed to settle. The supernatant was decanted into solvent waste. If necessary, each vial was stored overnight in a freezer. Each vial was uncapped and loaded into a sample tray of a Savant SpeedVac® (SPD121P). The SpeedVac® was set to run at 45° C. for 45 min at 0.1 vacuum setting and run for a total of 2-3 hours. Once complete, each sample was removed, and the powder contents of each vial were poured into a separate pre-weighed 4 mL vial. The mass and color of each supported catalyst was recorded. Each sample was capped, sealed with electrical tape, and stored in a freezer (−30° C.) for future use.

Catalyst C (comparative) was a DAVISON 948 silica supported catalyst made in a manner analogous to that described in U.S. Pat. No. 6,180,736 using MCN3.

Polymerization Examples 1-14 and 20-35

Polymerization examples 1-14 and 20-35 were homopolymerizations or ethylene/1-hexene copolymerizations carried out in a small scale slurry batch reactor using 0.3 mg of supported catalyst. In each of Examples 1-14 below, the indicated supported catalyst was tested in multiple polymerization runs using varying amounts of 1-hexene. For each run, the volume of 1-hexene used, the polymerization time (in seconds), the polymer yield (grams), and the catalyst activity (grams of polymer/grams catalyst·hr) are set forth below in Table 3.

For the polymer produced in each polymerization run (1-1 through 14-6), the following polymer properties were determined: DSC melting point (Tm, ° C.), C₆ content (weight %), and gel permeation chromatography (GPC) measurements of weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity index (PDI=Mw/Mn). These data are set forth in Table 4.

TABLE 3 Polymerization Run Data for Examples 1-14 1-Hexene Time Yield Activity Example Catalyst Run (μL) (s) (g) (g/g · h)  1 A 1-1 0 2700 0.0841 375 A 1-2 60 1734 0.0915 634 A 1-3 60 1698 0.0896 635 A 1-4 180 1106 0.0916 996 A 1-5 180 1161 0.0871 902 A 1-6 240 1337 0.0958 862  2 B 2-1 0 2701 0.0361 161 B 2-2 60 2700 0.0529 236 B 2-3 60 2702 0.0434 193 B 2-4 180 2700 0.0595 265 B 2-5 180 2700 0.073 325 B 2-6 240 2701 0.0794 353  3 C 3-1 0 2498 0.0887 427 (comparative) C 3-2 60 1386 0.0928 805 C 3-3 60 1332 0.0905 817 C 3-4 180 1001 0.0963 1157 C 3-5 180 927 0.0975 1265 C 3-6 240 871 0.0961 1327  4 D 4-1 0 785 0.0942 1443 (comparative) D 4-2 60 301 0.1057 4224 D 4-3 60 276 0.1066 4639 D 4-4 180 472 0.1034 2635 D 4-5 180 449 0.1019 2730 D 4-6 240 533 0.1082 2440  5 E 5-1 0 2435 0.0916 452 (comparative) E 5-2 60 1458 0.0913 753 E 5-3 60 1370 0.0894 785 E 5-4 180 968 0.0933 1159 E 5-5 180 951 0.094 1189 E 5-6 240 901 0.0957 1277  6 F 6-1 0 804 0.0857 1282 (comparative) F 6-2 60 614 0.0912 1785 F 6-3 60 639 0.0946 1781 F 6-4 180 305 0.1008 3980  7 G 7-1 0 2103 0.0718 411 G 7-2 60 1931 0.0934 581 G 7-3 180 1273 0.095 897 G 7-4 240 1209 0.0905 900 G 7-5 300 1373 0.0806 706 G 7-6 360 1783 0.0945 637  8 C 8-1 0 2286 0.0931 490 (comparative) C 8-2 60 1336 0.0959 863 C 8-3 180 834 0.093 1341 C 8-4 240 853 0.0982 1384 C 8-5 300 1024 0.098 1151 C 8-6 360 1201 0.0992 993  9 H 9-1 0 1221 0.0832 819 H 9-2 60 801 0.095 1426 H 9-3 180 612 0.0889 1747 H 9-4 240 653 0.094 1731 H 9-5 300 963 0.0968 1208 H 9-6 360 1552 0.1004 778 10 I 10-1  0 2144 0.0900 505 I 10-2  60 1050 0.0945 1082 I 10-3  180 720 0.1374 2296 I 10-4  240 879 0.0946 1294 I 10-5  300 1199 0.0988 991 I 10-16 360 1267 0.0989 938 11 J 11-1  0 1490 0.0898 725 J 11-2  60 977 0.0966 1188 J 11-3  180 616 0.0982 1917 J 11-4  240 693 0.0998 1732 J 11-5  300 660 0.0912 1663 J 11-6  360 985 0.1063 1298 12 K 12-1  0 1417 0.0841 714 K 12-2  60 718 0.0946 1585 K 12-3  180 505 0.1031 2454 K 12-4  240 611 0.1003 1974 K 12-5  300 646 0.0923 1718 K 12-6  360 756 0.1038 1652 13 L 13-1  0 1943 0.0917 567 L 13-2  60 1022 0.0922 1084 L 13-2  180 710 0.0829 1404 L 13-4  240 886 0.0948 1287 L 13-5  300 1133 0.1006 1068 L 13-6  360 1195 0.1019 1025 14 M 14-1  0 1787 0.0823 554 M 14-2  60 1488 0.0893 722 M 14-3  180 1139 0.0764 807 M 14-4  240 2377 0.0941 476 M 14-5  300 2506 0.0933 448 M 14-6  360 2702 0.0772 344

TABLE 4 Polymer Properties for Examples 1-14 Tm C₆ Average C₆ Mw* Mn* Example Catalyst Run (° C.) (wt %) (wt %) (g/mol) (g/mol) PDI*  1 A 1-1 135.6 0.0 0.0 321219 118934 2.7 A 1-2 128.8 1.5 1.1 373613 71811 5.2 A 1-3 128.7 0.6 — 363901 97561 3.7 A 1-4 123.0 6.0 4.8 361703 96026 3.8 A 1-5 123.1 3.6 — 332397 87410 3.8 A 1-6 121.0 5.2 5.2 373705 97453 3.8  2 B 2-1 137.3 0.0 0.0 1246580 293870 4.2 B 2-2 132.9 0.0 0.0 1025984 171713 6.0 B 2-3 133.2 0.0 — 1076751 260266 4.1 B 2-4 129.9 1.0 1.1 1065559 238354 4.5 B 2-5 130.1 1.2 — 1018277 240986 4.2 B 2-6 129.6 1.3 1.3 991678 220357 4.5  3 C 3-1 136.4 0.0 0.0 595381 264421 2.3 (comparative) C 3-2 125.4 2.1 2.2 482338 223939 2.2 C 3-3 125.6 2.4 — 462870 218017 2.1 C 3-4 117.9 5.6 5.6 505142 252255 2.0 C 3-5 117.9 5.7 — 546395 289367 1.9 C 3-6 115.8 6.8 6.8 588707 305332 1.9  4 D 4-1 133.7 0.0 0.0 161194 82837 1.9 (comparative) D 4-2 121.3 3.3 3.3 149610 79338 1.9 D 4-3 121.1 3.2 — 130375 59663 2.2 D 4-4 112.8 9.5 9.4 126041 52874 2.4 D 4-5 112.9 9.4 — 123863 54029 2.3 D 4-6 110.0 12.3 12.3 114236 43517 2.6  5 E 5-1 134.5 0.0 0.0 213627 117432 1.8 (comparative) E 5-2 126.4 0.8 0.7 201422 113941 1.8 E 5-3 126.4 0.5 — 195865 105193 1.9 E 5-4 119.5 4.1 4.3 212784 117234 1.8 E 5-5 119.7 4.5 — 216682 123496 1.8 E 5-6 118.0 5.5 5.5 212994 112489 1.9  6 F 6-1 136.2 0.0 0.0 731028 324702 2.3 (comparative) F 6-2 124.5 2.0 1.8 688610 275394 2.5 F 6-3 124.2 1.6 — 625363 281296 2.2 F 6-4 118.9 3.3 3.3 834890 401967 2.1  7 G 7-1 134.4 0.0 — 565851 94975 6.0 G 7-2 127.3 1.3 — 468137 69620 6.7 G 7-3 121.4 4.4 — 468154 49675 9.4 G 7-4 119.4 5.8 — 430957 48676 8.9 G 7-5 118.1 5.8 — 547283 61473 8.9 G 7-6 117.7 8.3 — 484250 37649 12.9  8 C 8-1 135.5 0.0 — 582120 249816 2.3 (comparative) C 8-2 125.0 2.3 — 445402 224890 2.0 C 8-3 116.9 5.2 — 503049 270886 1.9 C 8-4 114.7 6.5 — 511683 284654 1.8 C 8-5 112.9 7.7 — 532890 300264 1.8 C 8-6 111.4 7.3 — 567381 300355 1.9  9 H 9-1 134.0 0.0 — 212559 65518 3.2 H 9-2 126.2 2.5 — 188774 74117 2.5 H 9-3 120.2 8.7 — 213616 97520 2.2 H 9-4 119.3 8.1 — 188749 56541 3.3 H 9-5 118.9 9.3 — 174162 45894 3.8 H 9-6 118.6 10.8 — 177370 64046 2.8 10 I 10-1  133.6 0.0 — 286219 69798 4.1 I 10-2  126.1 1.6 — 204775 60186 3.4 I 10-3  118.9 6.4 — 305149 73872 4.1 I 10-4  119.3 6.8 — 231009 55784 4.1 I 10-5  119.1 7.7 — 222506 56351 3.9 I 10-6  118.5 9.7 — 181458 48585 3.7 11 J 11-1  134.2 0.0 — 331937 77848 4.3 J 11-2  127.2 1.3 — 191571 60764 3.2 J 11-3  121.7 4.2 — 218780 89037 2.5 J 11-4  120.4 7.1 — 204377 71439 2.9 J 11-5  120.1 6.8 — 194398 57488 3.4 J 11-6  119.2 9.3 — 197413 60169 3.3 12 K 12-1  133.2 0.0 — 189185 58940 3.2 K 12-2  126.2 2.3 — 150838 52847 2.9 K 12-3  120.9 2.9 — 162358 53083 3.1 K 12-4  119.8 7.4 — 167126 36177 4.6 K 12-5  119.9 7.9 — 131500 40618 3.2 K 12-6  118.8 10.8 — 121572 34141 3.6 13 L 13-1  133.1 0.0 — 205190 67914 3.0 L 13-2  126.4 1.4 — 182793 67760 2.7 L 13-2  121.7 6.5 — 201957 70194 2.9 L 13-4  120.8 8.2 — 205402 81291 2.5 L 13-5  120.3 10.3 — 179462 69349 2.6 L 13-6  119.5 12.6 — 158032 60122 2.6 14 M 14-1  132.7 0.0 — 487545 84679 5.8 M 14-2  123.8 2.6 — 720801 47954 15.0 M 14-3  117.3 6.1 — 577784 44938 12.9 M 14-4  115.4 7.9 — 545619 52289 10.4 M 14-5  113.6 9.2 — 445833 45443 9.8 M 14-6  108.9 11.0 — 419193 34943 12.0 *Mw, Mn, and PDI values in Taable 4 were determined using the Rapid GPC method.

As illustrated by Examples 1 and 2 and comparative Examples 3-6, at similar C₆ wt % the polyethylenes produced by inventive Catalyst A (MCN1) and inventive Catalyst B (MCN2) generally have significantly higher PDI values (i.e., broader MWD) than the polyethylenes produced by comparative Catalysts C, D, E, and F (see FIG. 1). Comparative Example 4 shows that Catalyst D, prepared with MCN4, which has a sterically less hindered 3-(2-ethylhexyl)-indenyl group combined with an indenyl, produced a polyethylene with a narrower MWD than that produced by inventive Catalyst A. Further, Examples 1 and 2 and comparative Example 5 shows that Catalyst E, prepared with MCN5, which contains 3-(1-phenylethyl)-indenyl and Me₄Cp groups, produced polyethylene with a narrower MWD under similar polymerization conditions.

Also seen from Table 4 and FIG. 1, inventive Catalyst B (MCN2), which is the dimethylsiladiyl analog of inventive Catalyst A (MCN1), has a somewhat lower 1-hexene incorporation capability than that of inventive Catalyst A (see FIG. 2). It is noteworthy that when the 3-substituted indenyl groups of Catalyst A are replaced with n-BuCp groups, thereby producing a structure corresponding to comparative Catalyst F, polyethylenes with much narrower MWD are obtained (see FIG. 1). Thus, it appears that by bridging a branched alkyl substituted indenyl group (e.g., 3-sec-pentyl-indenyl) with a smaller indenyl fragment (e.g., 3-Me indenyl) (as, for example, in Catalyst B), it is possible to obtain a catalyst that produce polyethylene with a much broader MWD than can be achieved utilizing bridged n-BuCp groups (as in Catalyst F), while at the same time maintaining reasonable comonomer incorporation molecular weight capability.

A comparison of Example 7 with Example 1 (Catalyst G vs. Catalyst A), or a comparison of Example 10 with Example 9 (Catalyst I vs. H), illustrates the concept that it is possible to obtain polyethylene with an even broader MWD by replacing the 3-(2-pentyl)-indenyl group of MCN1 or MCN8 with the 3-alkyl substituted 1,5,6,7-tetrahydro-s-indacenyl group of MCN7 and MCN9. For example, inventive Catalyst G (MCN7) produced polyethylenes with significantly broader MWD across the C₆ wt % incorporation range of 0 wt % to 8.3 wt % in comparison to Catalyst A. This is shown by PDI values as high as 6.0-12.9 for inventive Catalyst G in comparison to PDI values of 2.7-5.7 for inventive Catalyst A (see Examples 1 and 7 in FIG. 3). Both inventive Catalysts A and G, however, did produce polyethylenes having higher PDI values across the C₆ wt % incorporation range and comparative Catalyst C (see Examples 1 and 7 and comparative Example 3 in FIG. 3). In addition, as illustrated in Table 4 and FIG. 4, polyethylenes produced by inventive Catalyst G also have a higher weight average molecular weight than the polyethylenes produced by inventive Catalyst A under similar 1-hexene feed and other polymerization conditions. Similarly, inventive Catalyst I (MCN9) produced polyethylenes having a higher weight average molecular weight, as well as a broader MWD, in comparison to Catalyst H, although to a lesser extent (compare Examples 9 and 10 in FIGS. 5 and 6).

Catalyst J (MCN10) corresponds to a structure in which the indenyl group of Catalyst H (MCN8) has been replaced with a 1,5,6,7-tetrahydro-s-indacenyl group. Although Catalyst J appears to have produced smaller increases in Mw in comparison to Catalyst H (compare Example 11 with example 9 in FIG. 6) and smaller changes in MWD breadth in comparison to Catalyst H (compare Example 11 with example 9 in FIG. 5), Catalyst J did produce broader MWD polyethylenes across a range of C₆ feed amounts in comparison to comparative Catalyst C (see Example 11 and comparative Example 8 in FIG. 5).

Polymerization Examples 15-18

Examples 15-18 were conducted in a lab-scale gas-phase reactor. Polyethylenes having a broad or bimodal MWD were produced by both catalysts, but Catalyst G produced polyethylenes having a broader MWD and higher weight average molecular weight than Catalyst A under similar polymerization conditions. GPC-4D analysis was carried out on the polyethylenes produced by each catalyst. The results are set forth in Tables 5 and 6 and their respective GPC-4D plots are shown in FIGS. 7A-D. Interestingly, the g′vis values of the polyethylene produced by Catalysts A, G, and H are about 1.0. For comparison, catalyst N with 2-iPr substitution leads to a polyethylene with g′ of 0.88, under similar polymerization conditions.

The second melt DSC for resin in Example 18 by Catalyst N is shown in FIG. 13. Extensional viscosities at 130° C. and 150° C. versus strain rate are shown in FIGS. 14A and 14B. A small amount of strain hardening is discerned for this resin at both temperatures.

TABLE 5 GPC-4D Data for Polyethylenes Produced in Lab-Scale Gas-Phase Reactor at 85° C. Polymerization Catalyst Yield Activity C₆ Mw Example Catalyst Conditions Amount (mg) (g) (g/g · h) (wt %)^(†) (g/mol) Mw/Mn g' _(vis) 15 A 1.5 H₂/C₂ 52.9 64.6 1221 5.8 123,000 8.2 1.03 (ppm/mol %); 0.02 C₆/C₂ (mol/mol) 16 G 2 H₂/C₂ 39.6 24.8 626 5.5 171,000 11.4 1.05 (ppm/mol %); 0.02 C₆/C₂ (mol/mol) 17 H 2 H₂/C₂ 39 110.2 2826 6.4 62,717 5.2 1.02 (ppm/mol %); 0.016 C₆/C₂ (mol/mol) 18 N 2 H₂/C₂ 25.5 38.4 1506 10.0 98,284 7.8 0.88 (ppm/mol %); 0.016 C₆/C₂ (mol/mol) 19 J 1.5 H₂/C₂ 39.2 112.9 2880 7.3 64883 4.0 0.98 (ppm/mol %); 0.02 C₆/C₂ (mol/mol) ^(†)As determined by GPC4D.

TABLE 6 ¹H NMR Characterization of Polyethylenes Produced in Examples 15-18 Methyl/ Vinylenes/ Trisubstituted Vinyls/ Vinylidenes/ total unsaturation/ Example Catalyst 1000C 1000C olefins/1000C 1000C 1000C 1000C 15 A 10.7 0.06 0.03 0.39 0.04 0.52 16 G 10.3 0.06 0 0.36 0.06 0.48 17 H 12.5 0.09 0.1 0.34 0.07 0.60 18 N 17.9 0.16 0.21 0.1 0.14 0.61 19 J 12.9 0.13 0.16 0.29 0.06 0.64

Cross-fractionation chromatography (CFC) data show that broad/multimodal composition distribution polyethylene products have been produced in Examples 15, 18 and 19.

TABLE 7 Ethylene Polymerization and Ethylene 1-Hexene Copolymerization Using Supported Catalysts C and O to AC. 1-Hexene Time Yield Activity Mw* Mn* Tm C6 Example Catalyst (μL) (s) (g) (g/g · h) (g/mol) (g/mol) PDI* (° C.) (wt %) 20 C 0 2668 0.0862 388 590361 292532 2.0 136.6 0.0 C 60 1409 0.0948 809 442995 236080 1.9 125.5 2.1 C 120 1064 0.0839 948 487050 255280 1.9 120.5 5.1 C 150 1028 0.0944 1104 494901 254640 1.9 119.1 4.8 C 180 1111 0.0952 1031 531880 307726 1.7 118.1 5.3 C 210 1042 0.0986 1138 509437 289388 1.8 116.8 6.1 21 O 0 2700 0.0749 334 286946 112437 2.6 134.6 0.0 O 60 1271 0.093 880 207421 100642 2.1 125.4 3.8 O 120 688 0.0882 1541 209398 106930 2.0 122.1 5.7 O 150 798 0.0924 1392 228836 108966 2.1 121.2 6.8 O 180 811 0.0916 1357 194960 89529 2.2 120.7 9.3 O 210 1050 0.0967 1107 211598 105756 2.0 120.0 9.5 22 P 0 1027 0.0893 1045 299551 69035 4.3 134.7 0.0 P 60 598 0.0974 1958 256675 52456 4.9 127.2 2.9 P 120 301 0.0902 3606 332814 90076 3.7 122.8 4.9 P 150 348 0.1039 3586 324647 79391 4.1 121.9 5.6 P 180 446 0.0988 2663 283225 72786 3.9 120.7 6.0 P 210 662 0.0978 1776 338338 63317 5.3 121.1 6.4 23 Q 0 1214 0.0865 857 285757 52652 5.4 133.6 0.0 Q 60 702 0.093 1592 245168 46173 5.3 126.3 2.8 Q 120 521 0.096 2216 244773 65646 3.7 122.2 5.0 Q 150 590 0.093 1895 252342 84436 3.0 121.5 5.7 Q 180 588 0.088 1800 269646 68384 3.9 120.6 6.6 Q 210 730 0.091 1500 287214 59432 4.8 119.3 7.4 24 R 0 1634 0.0755 556 307896 89351 3.4 134.2 0.0 R 60 705 0.0815 1390 232361 88370 2.6 125.7 4.8 R 120 435 0.0854 2363 274670 92231 3.0 121.5 6.7 R 150 460 0.0952 2490 291523 82185 3.5 120.5 7.8 R 180 478 0.0893 2247 248611 87549 2.8 119.0 9.4 R 210 535 0.0886 1990 265821 77853 3.4 118.4 9.5 25 S 0 1567 0.0826 634 430670 51369 8.4 134.6 0.0 S 60 904 0.0913 1214 290905 65831 4.4 126.8 2.1 S 120 522 0.0801 1845 307096 59111 5.2 123.3 4.4 S 150 514 0.0924 2162 322766 81912 3.9 122.3 5.0 S 180 504 0.0937 2235 366661 73137 5.0 121.5 5.6 S 210 641 0.1056 1980 317497 43830 7.2 120.9 6.1 26 T 0 2585 0.0894 416 935792 348475 2.7 135.9 0.0 T 60 2701 0.0725 323 666081 333211 2.0 123.8 4.5 T 120 2701 0.0424 189 644669 352791 1.8 120.7 6.4 T 150 2701 0.0358 159 632317 333519 1.9 119.7 8.6 T 180 2701 0.0312 139 654385 307665 2.1 119.4 8.1 T 210 2701 0.0224 100 696617 342136 2.0 118.7 9.1 27 U 0 1634 0.0755 556 307896 89351 3.4 134.2 0.0 U 60 705 0.0815 1390 232361 88370 2.6 125.7 4.8 U 120 435 0.0854 2363 274670 92231 3.0 121.5 6.7 U 150 460 0.0952 2490 291523 82185 3.5 120.5 7.8 U 180 478 0.0893 2247 248611 87549 2.8 119.0 9.4 U 210 535 0.0886 1990 265821 77853 3.4 118.4 9.5 28 V 0 1363 0.0900 794 212366 67449 3.1 133.7 0.0 V 60 667 0.0980 1767 188992 63837 3.0 126.4 3.3 V 120 424 0.0892 2531 210059 70183 3.0 122.7 5.1 V 150 512 0.0950 2231 213181 74417 2.9 121.6 6.3 V 180 714 0.0960 1616 194607 63469 3.1 120.7 7.4 V 210 1230 0.0915 894 177434 55540 3.2 121.1 6.3 29 W 0 1719 0.0822 575 681859 196248 3.5 134.3 0.0 W 60 904 0.0939 1249 591755 159885 3.7 123.3 2.9 W 120 755 0.0949 1511 688711 150125 4.6 118.7 5.8 W 150 699 0.0945 1626 731454 150572 4.9 117.0 6.2 W 180 627 0.0882 1691 757843 183958 4.1 116.0 6.8 W 210 780 0.0990 1526 654540 157677 4.2 114.4 7.3 30 X 0 1719 0.0899 629 626380 170236 3.7 133.1 0.0 X 60 817 0.0951 1399 481704 155758 3.1 122.8 3.0 X 120 603 0.0822 1639 517135 141330 3.7 117.7 6.6 X 150 971 0.0961 1190 600313 136640 4.4 115.9 6.9 X 180 1095 0.0981 1077 478561 125374 3.8 113.9 7.9 X 210 1383 0.0941 818 397552 95204 4.2 112.9 8.4 31 Y 0 1482 0.0802 651 639369 110633 5.8 132.8 0.0 Y 60 822 0.0954 1395 488098 138596 3.5 122.0 2.7 Y 120 483 0.0801 1994 505616 106217 4.8 116.7 6.2 Y 150 673 0.0953 1703 538398 87737 6.1 114.1 8.1 Y 180 980 0.1030 1264 539122 113668 4.7 113.6 8.4 Y 210 1244 0.1025 991 523399 119358 4.4 111.1 8.4 32 Z 0 1719 0.0903 632 257465 58419 4.4 134.0 0.0 Z 60 898 0.0936 1253 209642 74612 2.8 126.4 3.1 Z 180 890 0.0915 1237 229162 83300 2.8 120.8 7.1 33 AA 0 1446 0.0835 694 511669 135283 3.8 132.9 0.0 AA 60 741 0.0926 1502 581772 165801 3.5 119.5 4.0 AA 180 886 0.0985 1338 502834 167206 3.0 109.0 9.3 34 AB 0 1366 0.0907 798 577950 186751 3.1 132.2 0.0 AB 60 593 0.0948 1921 550429 156157 3.5 119.2 4.6 AB 180 1139 0.0763 806 339968 145236 2.3 108.7 9.7 35 AC 0 1909 0.0835 526 305534 68799 4.4 129.3 0.0 AC 60 1091 0.0962 1060 243098 85766 2.8 126.7 2.4 AC 180 576 0.0976 2037 253534 63100 4.0 121.5 5.4 AC 240 628 0.0947 1812 275528 57739 4.8 119.7 6.1 AC 300 566 0.0941 2000 261808 53456 4.9 119.7 7.8 AC 360 732 0.1026 1686 256808 53803 4.8 118.7 9.3 *Mw, Mn, and PDI values in Table 4 were determined using the Rapid GPC method.

Polymerization Examples 36-40

Examples 36-40 were conducted in a lab-scale gas-phase reactor using General Procedure-2. Polyethylenes having a broad MWD (PDI 3.8-5.7) were produced by inventive catalysts with very good 1-hexene incorporation capabilities. Cross-fractionation chromatography (CFC) data show that polyethylene products with multimodal composition distribution have been produced in Examples 36 and 38 using inventive catalysts (FIGS. 11 and 12).

TABLE 8 GPC-4D Data for Polyethylenes Produced in Lab-Scale Gas-Phase Reactor at 85° C. Polymerization Catalyst Yield Activity C₆ Mw Example Catalyst Conditions Amount (mg) (g) (g/g · h) (wt %)^(†) (g/mol) Mw/Mn g' _(vis) 36 V 4.01 H2/C2 20.0 54.5 2725 13.1 99220 4.8 0.98 (ppm/mol %); 0.0256 C6/C2 (mol/mol %) 37 Z 3.11 H2/C2 21.1 29.3 1386 11.4 97613 5.6 1.00 (ppm/mol %); 0.0260 C6/C2 (mol/mol %) 38 R 2.99 H2/C2 20.0 11.4 570 10.4 123199 3.8 1.02 (ppm/mol %); 0.0288 C6/C2 (mol/mol %) 39 S 2.25 H2/C2 29.4 24.8 844 9.3 117972 5.7 1.00 (ppm/mol %); 0.0275 C6/C2 (mol/mol %) 40 O 3.56 H2/C2 29.0 45.0 1552 11.1 101846 4.2 0.98 (ppm/mol %); 0.0230 C6/C2 (mol/mol %) ^(†)As determined by GPC4D.

TABLE 9 ¹H NMR Characterization of Polyethylenes Produced in Examples in Table 8. Methyl/ Vinylenes/ Trisubstituted Vinyls/ Vinylidenes/ total unsaturation/ Example Catalyst 1000C 1000C olefins/1000C 1000C 1000C 1000C 36 V 22.1 0.21 0.21 0.31 0.04 0.77 37 Z 21.2 0.16 0.23 0.22 0.11 0.72 38 R 18.7 0.14 0.17 0.15 0.02 0.48 39 S 16.3 0.14 0.20 0.29 0.05 0.68 40 O 19.5 0.13 0.25 0.12 0.04 0.54

All documents described herein are incorporated by reference herein for purposes of all jurisdictions where such practice is allowed, including any priority documents, related application and/or testing procedures, but only to the extent that such documents are not inconsistent with the text of the present disclosure. As is apparent from the foregoing general description and the specific embodiments, while forms of the present disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, it is not intended that the present disclosure be limited thereby. Likewise, the term “comprising” is considered synonymous with the term “including.” 

We claim:
 1. A catalyst compound represented by Formula (I):

where M is a group 4 metal, R³ is a C₃-C₄₀ branched alkyl, wherein the branched alkyl group is branched at the α-position, R^(3′) is hydrogen, methyl, ethyl, or a group containing three or more carbon atoms having the formula CH₂R′, where R′ is an alkyl, aryl, or silyl group; each of R², R⁴, R⁵, R⁶, R⁷, R^(2′), R^(4′), R^(5′), R^(6′), and R^(7′) is independently hydrogen, a C₁-C₄₀ substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, alkoxyl, halogen, or siloxyl, or one or more of R⁴ and R⁵, R⁵ and R⁶, R⁶ and R⁷, R^(4′) and R^(5′), R^(5′) and R^(6′), and R^(6′) and R^(7′) are joined to form a completely saturated, partially saturated, or aromatic ring, T is a bridging group, and each X is independently a halide or C₁-C₅₀ substituted or unsubstituted hydrocarbyl, hydride, amide, alkoxide, sulfide, phosphide, halide, or a combination thereof, or two of X are joined together to form a metallocycle ring, or two of X are joined to form a chelating ligand, a diene ligand, or an alkylidene.
 2. The catalyst compound of claim 1, wherein R³ is a C₃-C₄₀ branched alkyl represented by Formula (II):

where each R^(z) and R^(x) is, independently, a C₁ to C₂₀ alkyl group and R^(y) is hydrogen or a C₁ to C₄ alkyl group, preferably a C₁ to C₂ alkyl group.
 3. The catalyst compound of claim 1, wherein T is represented by the formula R⁸ ₂J or (R⁸)J₂, where each J is independently selected from C, Si, or Ge, and each R⁸ is independently hydrogen, halogen, a C₁ to C₄₀ hydrocarbyl or a C₁ to C₄₀ substituted hydrocarbyl group, and two R⁸ optionally form a cyclic structure including completely saturated, partially saturated, aromatic, or fused ring systems.
 4. The catalyst compound of claim 2, wherein R^(y) is hydrogen.
 5. The catalyst compound of claim 2, wherein each R^(x), R^(y), and R^(z) is different from any other R^(x), R^(y), and R^(z) such that the catalyst compound has a chiral center on the α-carbon of R³.
 6. The catalyst compound of claim 4, wherein R^(z) is n-propyl and R^(x) is methyl.
 7. The catalyst compound of claim 1, wherein one or more of R⁴ and R⁵, R⁵ and R⁶, R⁶ and R⁷, R^(4′) and R^(5′), R^(5′) and R^(6′), and R^(6′) and R^(7′) are joined to form a completely saturated, partially saturated, or aromatic ring.
 8. The catalyst compound of claim 7, wherein R⁵ and R⁶ are joined to form a partially saturated 5-membered ring.
 9. The catalyst compound of claim 1, wherein R^(3′) is methyl.
 10. The catalyst compound of claim 1, wherein each of R², R⁴, R⁵, R⁶, R⁷, R^(2′), R^(4′), R^(5′), R^(6′), and R^(7′) is hydrogen.
 11. The catalyst compound of claim 10, wherein R^(3′) is methyl.
 12. The catalyst compound of claim 1, wherein J is Si and R⁸ is a C₁ to C₄₀ hydrocarbyl or a C₁ to C₄₀ substituted hydrocarbyl group.
 13. The catalyst compound of claim 1, wherein each R⁸ is a methyl group.
 14. The catalyst compound of claim 1, wherein M is Zr.
 15. The catalyst compound of claim 1, wherein each X is a halide.
 16. The catalyst compound of claim 1, wherein each X is chloride.
 17. The catalyst compound of claim 1, wherein the catalyst compound represented by Formula (I) corresponds to any one of the following structures:


18. A catalyst system comprising an activator and the catalyst compound of claim
 1. 19. A catalyst system according to claim 18, wherein the catalyst system utilizes a single catalyst compound.
 20. The catalyst system of claim 18, wherein the catalyst system comprises a support material.
 21. The catalyst system of claim 20, wherein said support material is silica.
 22. The catalyst system of claim 18, wherein the activator comprises one or more of alumoxanes, aluminum alkyls, and ionizing activators.
 23. A method of polymerizing olefins to produce at least one polyolefin composition, the method comprising: contacting at least one olefin with the catalyst system of claim 18; and obtaining a polyolefin.
 24. A method of polymerizing olefins to produce at least one polyolefin composition, the method comprising: contacting two or more different olefins with the catalyst system of claim 18; and obtaining a polyolefin.
 25. The method of claim 23, wherein said at least one olefin is ethylene.
 26. The method of claim 24, wherein said two or more olefins are ethylene and 1-hexene.
 27. The method of claim 23, wherein said polyolefin has an Mw/Mn of about 3.0 to about 13.0.
 28. The method according to claim 27, wherein said polyolefin has an Mw/Mn of about 4.0 to about 13.0.
 29. The method according to claim 28, wherein said polyolefin has an Mw/Mn of about 6.0 to about 13.0.
 30. The method of claim 23, wherein said polyolefin is linear low density polyethylene.
 31. The method of claim 23, wherein said polyolefin has total unsaturation/1000 C greater than 0.25.
 32. The method of claim 23, wherein said polyolefin has g′_(vis) of about 0.9 to about 1.10.
 33. The method of claim 23, wherein said polyolefin has g′vis of from about 0.98 to 1.0.
 34. The method of claim 23, wherein said method is carried out in a gas phase or slurry process.
 35. A catalyst system comprising an activator and the catalyst compound of claim
 2. 36. A catalyst system comprising an activator and the catalyst compound of claim
 17. 37. A method of polymerizing olefins to produce at least one polyolefin composition, the method comprising: contacting at least one olefin with the catalyst system of claim 35; and obtaining a polyolefin.
 38. A method of polymerizing olefins to produce at least one polyolefin composition, the method comprising: contacting at least one olefin with the catalyst system of claim 36; and obtaining a polyolefin.
 39. The catalyst system of claim 35, wherein the catalyst system comprises a support material.
 40. The catalyst system of claim 36, claim 17, wherein the catalyst system comprises a support material.
 41. The method of claim 30, wherein the is linear low density polyethylene is formed into a biaxially oriented film.
 42. The method of claim 23, wherein said polyolefin is formed into a biaxially oriented polyethylene film wherein said polyolefin is linear low density polyethylene.
 43. The method of claim 23, wherein the polyolefin produced herein has a multimodal composition distribution. 